ae SENKEN ed GROUP TRAINING COURSE ON MINERAL PROCESSING AND METALLURGY in the Research Institute of Mineral Dressing and Metallurgy (SENKEN) Tohoku University Sendai 980, Japan APPLIED THERMODYNAMICS IN EXTRACTIVE METALLURGY AKIRA YAZAWA Japan International Cooperation Agency The Government of Japanae SENKEN / GROUP TRAINING COURSE ON MINERAL PROCESSING AND METALLURGY in the Research Institute of Mineral Dressing and Metallurgy (SENKEN) Tohoku University Sendai 980, Japan APPLIED THERMODYNAMICS IN EXTRACTIVE METALLURGY AKIRA YAZAWA Japan International Cooperation Agency The Government of JapanCONTENTS I General Review I-1. Thernochemistry 1-1 Conservation of Energy 1-2 Heat Capacity 1-3 Change of Heat Content 1-4 Heat of Reaction I-2. ‘the Concept of Chemical Equilibrium I-3, Several Primary Laws on Chemical Equilibrium 3-1 Nenry's Law and Law of Distribution 3-2 The law of Hass Action 3-3 Phase Rule II Calculation of Equilibrium II-1. Affinity and Second Law of Thermodynamics 1-1 Affinity 1-2 The Second Taw of Thermodynamics and Entropy 1-3 Free Energy 1-4 Relation between Free Energy and Equilibrium constant II-2. Calculation of Change of Free Energy 2-1 Free Energy Equation 2-2 Variation of Equilibrium Constant with Temperature 2-3 Free Energy - Temperature Diagram III Activity TII-1, Solution III-2. The Definition of Activity TIT-3. Activity in High Tewperature Melts and it Quantitative Relation with IIT-4, Activities in Heterogeneo Phase Diagram s Bquilit IV Thermodynamics of Hydrometallurgy IV-1 Temperature Dependence of Physico-Chemical Properties in Aqueous Solutions IV-2 Activities in Aqueous Solutions 2-1 Expression of Activity 20 20 2 23 24 25 25 30 32 37 37 392-2 Activity Coefficients of Nonelectrolyte 2-3 Activity of Strong Electrolyte IV-3 Ion Equilibria in Dissolution-Precipitation Reaction 3-1 Dissolution-Precipitation Reaction of Hydroxide 3-2 Effect of Complex Formation Iv-4 Oxidation and Reduction IV-5 Potential-pH Diagram V Chemical Potential Diagrams V-1 Special Diagrams between pil and Potential V-2 Potential Diagrams for Pyrometallurgy V-3 Chemical Potential Diagram for Iron-Sulfur-Oxgen System 3-1 Introduction 3-2 Behavior of Iron Sulfides in Sulfuric Acid Leaching Process 3-3 Equilibrium Relations of The Fe-S-O system in The Roasting Process 3-4 Equilibrium Relations of The Fe-s-o system at Matte Smelting Temperature 3-5 Equilibrium Relation of The Fe-S-O system at 1600 C 3-6 Summary References 56 58 60 60 62 63 65 68 68 72 79 79 79 81 84 87 89 89I General Review T-1, ‘Uhermochemistry }=1_Conservetion of Fnergy The occurrence of a chemical reaction is always accompanied with the adsorption or liberation of energy. In the combustion of methane (natural gas), for example, evolution of @ considerable amount of cnergy is observed. CHy + 202 = COp + 7H20 stotel energy. x oY ew . From such facts, we can suppose that every form of matter contain certain amounts of energy, i.e., x,y,2,¥3 bul ve do not know total eneray of methane gas itself (x) or of the water produced (w), cte. However, if the products of @ reaction contain less encrgy than Une reactants do, as like the above example, (z +) < (x+y), the difference must be Liberated during the re~ action, and we can measure the cnergy outpul as heat and work. To express the energy change in the reacLion, shall we use the symbol AH, that is, (g +w) - (x+y) = AR, In the present casc the value of AR is negative. AS you know, such kinds of energy change are easily determined by, for example, bob calorimeter. Baned upon the measurement, we can express Uhe change as follows: CHy(g) + 202(g) = CO2(g) + 2it20 (1) bB29e = -211,700cal ‘This equation signifies that when 1 mol, that is, 16.0hg of methane is burned in a constant vloume calorimeter to produce COz and liquid state 120 under constant temperature of 298°K or 25°C, the quantity of heat flowing out of the calorimeter is 211,700cal. In the above procedurc, so called mw of conservation of energy or the firct lew of thermodynamics is already approved unconsciously. Although il is not necessary to explain for you the significance of the law, in the sbove case JE corresponds to the change of internal energy, and the decrease in internal energy is just compensuled with the evolution of the heat. As you know, heat is one of the commonest forms of energy, being the most important one for metallurgists. It is somctimey called the lowest form of energy because other forms are readily converted into it. However, the reverse transformation is not so easy and is subject to limitations pre- seribed in the second lew of thermodynamics. In general, using the no- tation W for work, we can express the following relation. ak =Q-W (1)Tn the sbove example, W= 0, because the reaction proceeds under constant volume. However, since the most metallurgical processes arc taking place under constant pressure, heat coulenl or enthalpy, 4, is used instead of #, more conveniently. Wek + pv (a) Absolute valucs of ll ere also not known but Lhe values relative to ¢ reference lempernture such as 298°K or O°K, (iy - zee), or differences accompanying some changes (AH) can be determined. In general, NE Q- w+ paV (1-3) When the work is only expansional one, Wes pav AE = @p jn usual chetcsl reactions, Qp signifies reaction heat In Lhe Table 1-1, you can sco some useful conversion factors among various kinds of energy units. Table 1-1. Conversion Factors for Buerger Units man | ken erg joule cal ters 1 e107 0.239%107? | 9.8re107?® | 0.102107? 1 joule 1*107 1 0.239 0.00987 0,102 Veal 4, 180x107 4.1840 1 0.04129 0.4267 1 Enatm | 1.0132«10° 101.32 2h .216 i 10,333 1 Ke-m | 9.806*107 9.806 2.33 0.09678 1 KWH = 1,341 HP-hr = 3.6-10% joule = B60i21cal; 1 Btu = 252.2cal. 1 joule = 107 erg = 1 watt-sco = 1 volt-coulomb Heat Capacity TL not necessary to repeat the explanations about specific heat and heat capacity themselves. In the field of metallurgicul Lhermodynamica, molar heat capscity under constant pressure, Cp, is used conveniently, The heat capacity of a substance usually increases with increasing temper- alure, The varistions eve illustreted for several Lypical sybstances in get-t, Tt is observed in Fig. 1-1 that an abrupt change occurs at « trans: formation or melting temperature. Following experimental equations sre conmonly cuployed in order to cxpress the variation with temperature, cps ature ot? (1-4)Temperature deg F HBSSSERPESERS SER As a a aod “emperature, des © Fig V1. Molo heat copacty of typeat wbsances. Cpsat pre cp 2 (1-9 cptatvr- cP (1-6) For metallurgical usage, it is generelly snid that the type of eq. (1-6) is the most profitable, and values of a, b, and ¢ for a number of substances are summarized by Kelley"), Several examples are tubulated in Table 1-2. 1-3 Change of Heat Content As has already been discussed, it is difficult, and also unnecessary for us, to know the wbsolute value of heat content, and, for parcieu! use, St will be enough if we can obtain ils difference, dll, Uke change of hest in the process metallurgy can be explained almost perfectly bi sed upon the following data concerning with change of heat content. (1) 4H originated in the variation of temperature of pure substance. 1) K, K, Kelley: U.S. bureav of Mines Bull. 464, 1949, Contributions to the data on theoretical metallurgy.able 1-2 selected Heat Capacity and Feat Context Equations — - jobs “te a z = substance a ene} a temp. ror gH ia Trans. : wr ee eae = Con esr Tt, tating ware bmacriee S| an| se| on |ee| Sooo - — —_ ona mel te] S| cee | ieee os substance . a | em} a tes ‘ercor! af in Tans, =o oe rie oe = _ceraree is | [Teceee jevrerlam in ane, EL) tae | Ee | S| Cane | Sa = ae [setae] em | sie [mii | es) as cw an| 40) — | om | saa = ao oe] ae FS coo, (an) 8) pa] aoe = ae el fe | EP |e | BER BR| >) 2 [ak) Rey l s acl |e? | cae =| 2/| es @ au) > | 2 | les) amo = eis) se = | maa) zeae] 2 | oo 804 an| no} — |-on| seals | — Pt s) 2 (al msi) @ ae ea = 1 cbt rn ze) S [ous | eee deh on no Se] s|-Sa | asel weanl a | SS ae 2 i te) Sy He] AS] 8] ae) aot | ee mee me = jhe | “ee |i |S nO ae | im) = [sa | iwoe| t | te oe is) cw [cu | om] i| = Re we| 2? (= [SB] lec | ba a a8) Sey = ne ae| = | 2 [28] ie} d | Maco 2 a Ee | Ra] am | = | rao! ‘Sas ] a | ao = | ewe} BEY | a meQ | 88) te] = a) Suet: | ae m0 = is Manji | = mee | BS] 2? = | se] aes | | tae ina} eli) tf Rov | nw | ae 28) 23] i | oe | aw) cme | pee les | > Fech D nal — yp | soup] os) = an cae | Bee it] o Foekan | itn] te pee || ices te| cee! She ( i) 2 ae au | as ey | as || ave a | mS | | up sali) & ae | =f oet fae) i | 2 me ee[ ’?] = oe) casts | Eis eli) Feerao | ar | aa! = ae perry mali! @ meg RRL UE) Dj we | Bm | = eet | Bl! | we ae | ae] Oh on (soo) ie [Epo one ca | ne tel sa |ta{ coe] meee lax] = treet ‘sa |2| = tt tu) te | ces | cme] dee | es] = cao @) mum ft) > nod) wa |<] 2") Tos | mom | ce) aR eSr0 brim [te] = ti tw | am | ian | Sie | 3). oo mal tee te} dei" (rel Sep) t oa i =| a(n) @ oe iS) 2] = |p Srey) = Sa mun | P| - M 8) iS] ca] cah] Bre] it | as ao cen | i | uw wo se] Se) amps) Raha | OS ae meliy & Meo | ae! ao] Te( cae] Soe los | o eos 2 toe” | eel asl Selce| Geese! = ea won| xs te ie, Mice) sts | is) 5 ae Bali | 3 may | inl BS] f oe Mos] i | om oo Em) in| ao | ne) mae! | me es 2 Se) oe | | =e ih) abl SP |oe) aim i | ao = [eal oe |t | = mo ae| | = fe | dem | a! S Bes 2 ae] =e ma | > | = [2fe | mecky | oo | ass cr cn|-oo| Boma] a | aw eo SSL S| 2 [el eStain | * | aT Te [om Te sew ee z aa ae Sisto | ae a aa | in Meee | pao os ma) = sho mh 3 ae! aa mee is ae} an misccey | am as | aa) ke Me .o 1 mts | xu on pa te | = seen ao ti aS) te Ned 1 zo| in Mow | ie ta | ie Maw be 1 az| in Nec 160 3 as | a0 neo 13 as Poh a no coy a an | ie mo Pa : tate Ncr@ | tn : ta foes ‘e ne Bo as ‘ iSO (@) ms : ow “a rf - ro in aft row te tle mo oe Tg no cs | ii S few st, iyo now soe | tps oes cr itl = nso ae a] ree ee i] ot pst | me} aw) -en| lam} gram | sf > su ea | 2? | cae) Belmd tof Ae Os | ay! Ta] foam ar] > Swe zal Le oem] Bie PPT etry sa! oan) im] Sete fi | o 23 ue) 2" | ch) atte | 1 oe mo SM {5 | oie) aoc Fa OE suns mal = | oa so os) iw) mm | Bim) a | sco | uo am | oe] geome | 2) seuto ta | 2s | oes} pea | as] = Sorcowy | Us| ate] 2" |i) ais 1] Seam | uo| au] > | le] Stee) as] 2 ante te) ee} ard so me PL geo [a je Seon in ne ie] Se Sema | me Se | Soe | aa prim) 3 | >(2) 4H originated in the change of aggregation sinte of pure sub- stances (3) all originated in the formation of compound from clements. (4) aH originated in the formation or dilution of solution. The last one is also important thooretically, and will be discussed later fon, bul comparing to the total heat content change in the metallurgical process, its amount ix quite small in general. Thus, shall we consider here about the other three kinds of aH. (1) In the fields of thermochemical and thermodynamical calculations, 25°C(298°K) is mostly selected as the reference temperature. When one mole of a certain substance is heated from 298°K to TSK, the change of heat content is expressed as follows: Hp - Hage = Cp(T-298) (4-7) Although in practical thermochemical calculetions mean specific heat is often used, precise equation can de obtained by integration of equation (1-6). Hy - Hose = aT + W/aet? +er +4 (1-8) Because the numerical values of a are also listed in Table 1-2, the value Of Irilzg, is easily derivea, which corresponds to so-called sensible heat in the ficla of technological thermochemistry. (2) As you know, the change of aggregation state is always accompanied by the change of heat content, that is heat of fusion, heat of vaporization, heat of transformation, ete, Gome of Uhem ure ulso listed in Table 1-2. When you wish to get the change of heat content from 298°K to °K tor certain cubstunve which has the chunge of aggregation etate at below T°K, the heat of transformtion is wlreudy included in the numerical constant d. For example, shall ve calculate the censible heate for one mole of liquid and solid copper at 1357°K which is the melting point of copper (1084°C). cule): By - Hage = 5.417 + 0.75 x107%7? - 1680 = TOkO cat Cu(1) : Rp - Hope = 7-50 - 20 10160 cal The difference, 10160 - TOMO = 3120 cal, corresponds to heat of fusion for copper. Now you can understand the profitability of this table, and can find boll of specific and sensible heats at arbitrary temperature withoul any complicated mathematical calculations. (3) The change of heat content, which ve should discuss sbout innext place, is so-called heat of formation, When one mole of a certain compound is produced at 25°C from its con: Litutionsl components, under constant presuure, All = -Qp, if the work is only expansional one. This corresponds to the heat of formation. For example, Clr) + 02(@) = Coa(g) A¥ege = -94050 cal The negative sign show that the reaction is exothermic one. The neat of formation for various compounds are given in able 1-3 °*9), Table 1-3 Heat of Vormation, AWa9e(keul/mole) cabstnee [tae euvetance| sn substance svn substance aw [eupem la paoe app ae mao tow | 6b Be maw | ts ABU yy |e 1x84 (lia) | 380.91 ate no" |e aske Mocleco [iat ancee Matos») 2% neon) Mu [sine ss Gace | a2 | Mois | Le was corm | o2| ee |e mos co [me] ano (aus | Ges) tua ey | #4 | Sacto) | 3 wont) cow Gacy | 6 | Sree x] 308 [SOK ena eat emi | ke | mow "| me) sce cath Ciao,” Jason] Maos om |s2tes | Sate co co8«e) reciecs) | a6 | Mas) [202 | Tie Gen feels | aun | Meade cy [acs | Tica co ho @s | smsco fae | ten tao, [tee | sinsoe [tat Tick co Goto x feo [ama | Moos [ims | tien Co ceconds reo, ir | ocr | oa] Torco cs teste [aa] son aw) Vad caus taster | 2321 New wae | we. cos rao [2.8 | Naso | 2 | Woe Cm80, Pet ts) |=a0 | save [m0], wo coy | 9888 ensnce rare [| xtra fue] asc | Re esac me | moc | aa | aso [205 co PEL MO EA Uae |e Gow oe x : Heul of formation from compound, #.g., Ca0+CO2=Ca00 2) Selceted Values of Chemical Thermodynamic Tropertics, U.S. Bur. of Standards, 1949. 3) J.P, Coughlin: U.S.Furcau of Mines, Bull 547, 1954.1-k Heat of Reaction Regarding to the calculation of heal. of reaction, so-called Hess's Law or law of constant heat summation is quite useful. From Table 1-3, for example, Fe30,(s) + kcolg) = 3Fe(s) + 4co2(s) (1-9) -267800 4(-26420) 9 (94050) Heae = 4({-9h050) - (-267800) - 4(-26420) 720 cal Fxothermic nature is confirmed for the reaction but not so strong. leat of formation of compounds are mostly determined based upon this principle. For cxemple, in order to determine the heat of formation of MaZag Mg + Pan = Mgzne ae the following three experiments should be carried out. (a) Mg + 2HCL = MgCl2 + Hy Alla, (o) 7m + 2HCL + uncle + Ip afb (oc) Mging + GHCL = MgOlz + 22nCle + 3H ae ‘Tas, Alix = QHa + 2aHb ~ Alle The problem often ariscs to find the heat of = reaction at some high temperature. Because eq.(1-8) can be used for cach participating substance, the following equation will be adaptable as a whole, = BHzog = dal + 1/2abT? + act? + ad (1-10) Shall ve derive the neat of reaction st 1000°C for the reaction of eq.(1-9). 3Ro(y) Hy ~ Hage = 14.55 T+ 4,50 x 10°8r? + 1170 CO Hy — Magy = 42.20 1 + 4,32 « 1079? + 8.16 x 108? - 1570h Fess: Hy ~ Hogg = 39.92 T + 9.43 x 1078T%+ 10.01 x 10847? - 16098 4co Hy ~ Hage = 27.16 T+ 1,96 x 1078T? + O.uL x 108? - 8420 Thus, for — Fe30,(s) + 4CO(g) = 3Foly) + WOO. AB ~ AHooe = -10.332 - 2.57 x 1079T? - 2,29 x 1089? + 998k T From the remults already oblained for eq.(1-9), Ally = 7264 = 10.331 = 2.57 x 10787? - If we calculate at 100°, bHya7y = -10230 ead Alga = -2720, 2.29 x 1087? Judging from the results obtained, this reaction represents larger heat evolution at high temperature. As you nce in this example, both of AHay9 and Ad are constant values, being s1 marized inte one constant, AHo. OH, = AHO + AAT + 1/Pab + act? G11)This is so-called Kirchhoff's equation. AH may be regarded as en extrspolated value for the heat of reaction at 0 absolutc, but will not be the actual valuc at O°K, since the equation for Oy, (1-6), is never appli- cable to such low temperature, T-2. The Concept ot Chemical Equilibrium Lewis and Randall") described in their famous text book as follows: “In all thermodynamics there is no concept more fundamental than the idea al non- of equilibrium." In order to apply thermodynamics Lo a precti forrous metallurgical process, it is of primary importunce to evaluate equi- librium state. Accordingly, Une concept of equilibrium is quite important for us, but from the standpoint of application, sometimes it seems to be somewhat ambiguous. Shell ve start the oxplanation with the Houdouard's equilibrium re- action vhich is the most intimate one for metallurgists. When CO gas is enclosed in a reaction chamber maintained at 600°C, some part of the gas msy dissociate into Oz and solid carbon as follows: peo 2 co, +¢ (1-12) On the contrary, if C02 and C are enclosed in the chamber and heated at 600°C, the reaction proceeds in the inverse direction (to left nana) to produce CO gas. When the reactions take place under a constant pressure are illustrated in Fig.1-2. Starting gas composi- of 1 atm, the processes 100 Fig.t-2 200 = cO+G (under 1 etm) CO tm) (a 408] 6t0” 700 600900 TOW Th Temperature (°C) 4) G. N, Lewis and M. Randall: Whermodynamics and the Free unergy of Chemical Substances, 1923,tions are represented with points 4 und b, respectively, and the reaetions proceed in the direction shown by arrows, that is the reaction (1-12) can proceed both directions, and the change of gas compositions ceases at point n, where the reaction rates are the same for both direction, Under tne given conditions, the concentrations of CO and COz at point m ure about 25 and 75 per cent, respectively, and not change sny more, he state as Like this is called chemical equilibrium. Recause the equilibrium gas compo- sitions change with temperature, so-celled Boudouard's curve is drawn under Tatm, as shown in Fig.t-2, Within the range of upper left of the curve, the reaction of (1-12) proceeds to the right hand, vhile within the limits of lover right, to the left hand. Although such of reaction is sometimes called reversible reaction, but from thermodynamical point of view, wll the chemical veuclions ere reversible. For example, the reaction 2Ha(e) + O2(g) = 2u20 (1-13) Proceeds to rignt hand almost completely, but when H,0 is heated at a certain temperature, dissociation of K,0 into ll und 0, can be slso expect- ed, though the amounts of Hy and 0, will be extremely small. Moreover, we can dis inguich between nomogeneous reaction, as Like (1-13), and heterogencous onen, tor example, notal-slug-gas, but within the respective phase, we can reasonubly Aiscuss homogencous reacLions, As has often been noticed, due to infinite slowness of reaction rate, Hy and 02 can coexisting without formation of Hj0 st room temperature, though Une reaction (1-13) should proceed to right hand. Tn such a esse it looks apparently an if the system was in a stable equilibrium state. We shail encounter with such examples especially in tne hydromotallurgical field, although extreme cuses are not so frequent in pyrometallurey because the reaction rate is repid in gencral at high temperature. Although we have to recognize the difference between Lrue and false equilibrium, in practical application, so-called metestable oystem is sometimes used convenienlly. You know typical example for the phase diagram of Fe-c system. Fansen is describing in his book) an follow: "There has been some difference of opinion as to whether the double diagram is justified. This point is not being trated hero; however, it 5) M, Hansen & K, Anderko: Constitution of Binary Alloys, 1958. =10-should be stressed that there iy no reasonable argument egainet not using the double disgran, since it offers @ convenicnt means of represcnting the observed behavior,” The similar example will be given Leter on, As another problem to be noticed, equilibrium state will be never in- fluenced by gravity, elasticity, surface tension, viscosity, amount or weight of phase, ete. For exemple, in the reaction (1-12), the the quantity of carbon particle does not give any influence on the equili- brium state. However, the physical properties which have been Just mentioned above, have a great influence upon tne time required to reach equilibrium state. TL is quite natural thet the analysis of prectical process should be done based upon both of kinetics and thermodynamics. I-3, Several Primary Lews on Chemical Lquilibrium Although there exsist numerous laws on chemical equilibrium, shall we discuss at first a fev primary laws in order to familiarize ourselves with the concept of metallurgical equilibrium. 3 Henry's Law and Lew of Distribution When Liquid and gas are coexisting in equilibrium state, the concen- tration of gas dissolved in liquid phase is in proportion to the partial pressure of gas at a definite temperature, That is, Py = EC, (1-14) where p, is partial pressure of the component # in guy ghase, Cy is concen- tration of A tissolved in Liquid phase, L is coefficiont which is constant alm definite temperature. his relation is well-known as Henry's law. Tt should be noticed thet in this case there exist following Lwo restrictions. Firstly, behavior of A should be ideal type in both phase of gas and liquid, In most metaLiurgical reactions, gas phase can be trentied as iden) state practically. Liquid phuse is not necessarily ideal, but Uenry's law may be applicable for dilute solution, As the second restriction, it is necessary that the nggregation states of A are the samo in both pha: eof gas and liquid. For example, Henry's law cen ve applied to absorption of hydrogen in squeous solution in autoclave, but anecan not be applied directly absorption in molten metals. Fxtension of Henry's law into general hetcrogencous cquilibrium system may be realized by use of the lav of distribution or Nemnst's lew. Suppose that the concentrations of A in two liquid phases which are equilibrating with each other aro C, and Ca,, and partinl pressures of A represented by cach liquid phase are py , pa, respectively. According to Henry's lew, Ay Ae e la ¢ = kee Pa a, Pap ~ U2 Sq, As a matter of fact, these tvo liquid phases coexist in equilibrium state, hus, they are kept under the gus phuse of the same composition, that Pa,= Page Bence, (1-15) L! is constant at a definite temperature, and is called digtribution coeffi cient. th can be applied not only to the system liquid-liquid, but also to Liquid-solid or solid-solid, vo restrictions explained in Henry's law are also valid. Distribution of FeO between molten stcol ana sleg is expressed as follows: Lpeo = £20 / (Feo) where, FeO and (Vc) arc concentrations in metal and slag phase, respective- dy + Constant value of Lp,, can de determined based upon fundanental Feo experiment. Following relation which has the sane content with above equation is cmployed in iron metallurgy. dogt [8 0] / O49) 1 = ~6.320/2 + 2.73 On the contrary, distribution of sulfur between molten s ecl and slag ered as is somowhat complicated. In molten steel, sulfur can be cons 8, but in iron metallurgy most part of sulfur is estimated to exist as CaS in slag. Accordingly, from the standpoint of distribution law, Lygg = us is doubiful, although in arse valid, but 15/Z(3) practice so-called desulfurization ratio, (#8)/S3, is often used, this FeG/(FeS) is of « problem wil] be diseussed a Little more lster on. 2 The law of Mass Action =12-As you already know, the lew of miss action for the reaction, AtbeceD (1-16) is expressed in general an follow a7 4 GIF a (a-17) a oR where, K is equilibrium constant and @ represent activity of each compo~ nen, Although you understand the concept of ncLivity, it will be explain= ed in detail later on, As hes elready been mentioned, in the most metal lurgicsl process gas phase can be supposed to be ideel. Hence, if partic~ ipating components are all gas species an Like eq. (1-13), muss action law is expressed as follows: -£ Payot week, fiers = SB (1-18) Po PatPR Pe Por Moreover, when the reaction takes placo in homogeneous condens concentration C(%) or mole fraction N is sometimes proportional to activity @, especially in @ilute solution. In these cases, following relations are also usable. (1-19) Arthough K,, > Ky and Ky are ali equilibrium constants, the numerical values are of course different. The law of mass action is very important for metallurgist, because, necording to this relation, we can judge in which direction and to what extent the proposed reaclion will proceed. ‘hermodynamics is a quite uscful fundamental theory which hes a very wide applicational field, and We can find many examples of metallurgical application not only in process metallurgy but also in metallograghy, heat treatments, foundry ete. Although there ex. demand, as far ae the practical application lo nonferrous-metullurgical bion as the needs of the case various lypes of applic processes is concerned, it is of primary importance to calculate and inter- pret the equation of mass action law. By the way, the law of mass action is derived essentially as the lew which valid in homogeneous phane, in order to apply it adequately to heterogeneous reaction, as 4 general rule, it should be used under combi- nation with the distribution law. citing practical metallurgical prob- aielems as examples, T'11 explain to you this relation. In the preceding paragraph, we have discussed some problems of guy ub- sorption. chal] we suppose that diatomic gas G), which is not dissociated at all in gas phase, is dissolving to some extent in equilibrating Liquid phase, and s park of it dissociates into monatomic stute in accordance with the reaction G2 = 2G. When the concentrations off element @ in gas and liquid phases arc (, and Ce, respectively, concentrations of undissociatea molecule in gas and liquid phases are Cand C2 (12), respectively. Distribution Inw for G; molecule is expressed az follot C/ C2 (1-0) L where, L is constant. In this case, we can apply mass action law to the reaction G, = 20 which cen be considered to take place in homogeneous Liquid phase. xr = (za)? C2(1-9) where, Kt is equilibrium constent. Combining both equations, a Gy Rokr" Toa } (1-20) a ‘Thus, we can apply mass action law to heterogeneous system. As a practical example, we can suppose the absorption of hydrogen in molten metal, where hydrogen dissociate completely into atomic state, that isa = Repre- senting hydrogen concentration in gas phase with pertiel pressure, k= O2WPy (1,21) Wanely, the solubility of hydrogen in molten-metal is in proportion to the squere root of partial pressure of hydrogen. Thus, we could derive so- called Sieverts" law. In the next plece, shall we suppose desulfurization of molten iron by Fe0-Cad slag. As has been mentioned in Uhe preceding paragraph, following equation is valid for distribution of Fes, Les = (FeS) / Fes Im the homogenious phase of molten slag, the mass action law is applicable to following equation. (Fes) + (Cao) = (cas) + (Feo) sales(Fe0) (cas) eS) (Cad) Because the most part of sulfur in sleg is supposed to be CaS when the ratio of Ca0/FcO s high in the slag, Une following reletion can be derived. This relation was confirmed by some experiments. Phase Rule As you already know, concerning with equilibrium in a heterogencous system, freedom F is represented with following equation by Phase Hulc. Fen+2-9r (1-23) wnere x is the number of phase and n is the component. Tn practical applications, the determination of number of n sometimes creates trouble~ some problems. in text book of physical chemistry the reaction CaCO: = (a0 + CO, is often quoted to explain this problem. is you know, the number of independent component in this system is two, although the number of chemical components in ordinary sense scoms to be three. To solve such kind of complications the following equation is sometimes used convenicntly. PeO+2-r-R-3 (1-24) that is, n=C-R-S (1-25) where, C is not "independent" component but is the number of al] components in actual existence, is the number of independent reversible resetions existing among those components, and S represents the number of restriction concerning with molar ratio relalion, Thus, for CaCO, = Cad + CO, C = 3, R=1,850; .'.n=2, Water is the typical example of one component system, ft high temperature, however, due to dissociation of H,0 , 4 small amount of Hp and 0, are also taken into account. 2H20(g) = 2Ha(g) + O2(e) (1-13) In this case, both of Hy and 02 are originated from #20, und mole ratio of Hig lo Op is always 2: + Thus, the number of independent component ie: n=3-1-15 1. In metallurgical experinents, gus mixture of Iz and Fy is often used to entublish the oxygen potenLial based upon the equilib -15-rium relation of (1-13). In this case, of course n = 2, though C = 3. In the next place ALL we discuss dissociation of copper oxide based upon the phase diagram repr nted in Fig.1-3-a, 8 £ F ¥ s 10 yo" Wao 11010" Ie a Pron (mete) o 2 quilibrium diagrams for Cu-O system 1 (a) Composition-temperature = (c-t) diegram & (b) Pressure-temporature (p-t) diagram (c) Composition-pressure (¢-p) diagram et 1230°C cuz0 = 20u + 1/202 (1-26) BCuO = Cuz0 + 1/202 (1-27) Undoubtedly, 2 = 2(Cu, 02), 5 when the reaclion takes place at below melt- ing temperature, in general, r = 3, for example, solids of Cuy0 and Cu and és phasc. Thus, F = 2+ 2-3 15 this indicates that the equilibrium established by defining of temperaturc, that is, al a definite tompera- ture, @ definite oxygen pressure (dissociation pressure) should be corre= sponding. uch relation is illustrated by the curve VIII in Fig. !-3-b 16+for (1-26) reaction and the curve I for (1-27), Fven in the molten phase, the sane reaction with, for exemple, (1-26), can be supposed, but sometimes the number of freedom is different. In the limit of In or Tz in Fig. 1=3+ a, F= 242-22, this is cxpressed in Fig.1-3-b with area, not with 3 and F curve. When two Liquid phases Iy and Ly are coexisting, r Tais corresponds to the curve VI in Fig.1-3-b and B in Fig. 1-3-c. Next, I'll shortly explain to you the molten slag of Fe0-Fe20;-8i0, Fe-Si-O system is including molten slag (Fe0-Fe,03-Si0,) system, Becmus w#as system, molten iron-slag-gas system, ete. depending on Une temperature and composition, it is quite important for both of iron and nouferrous Especially, fundamental knowlege about this slag system metallurgists is indispensable for nonferrous pyrometallurgists. Pig. 1-h is illustrating FeO: SiO; 20 40 Fig. t-l Isotermal diagram for F -Fe203-Si02 system at 1350 -u-isothermal section diagram at 1350°C for FeO-Pe20s-8i02 system, range S surrounded by ABCDA represents the molten slag cquilibrating with gas phase. When thie slag-gaa system iv coexisting with volié ailies, the slag compo- sitions are illustrated with line CD in Fig. 1-4 and corresponds to the case sorealled silica saturation, At that time, P= 3+ 2-3 = 2, thet is, at 1350°C, specification of any one of ny,, FeO, Si02, Fe09% ete, cotablieh the systom in equilibrium state. If the slag is saturuled with solid magnetite or metallic iron, the compouilion corresponds to line RC or AD et iO, and mag- 1350°C, Moreover, when the slag is saturated with both of § netite, for example, the system is monovarinnt that is F = 1, and the sleg g-t-k at 1350°C, composition is chown with point ¢ in Phase rule is of course more useful to metallurgical researcher in uni versity or institute Lan to practical enginecr. It is necessary to con- firm your experimental conditions by application of phase rule, and you will be able to understand its necesnity by solving exercises. -le--19-II Calculation of equilibrium Ti-1, Affinity and Second Law of thermodynamics 11 Affinity In order to get accus system, the oxplanstion is given In the preceding paragraph about severel tomed to the idea of metallurgical equilibrium laws with vhich you have long familiarized yourselves, although equilibrium ion lav. From eurly ages, the word state can be expressed by the mass 1 “affinity” has been used to express the intensity of the Lendency which the ec. In reaction proceeds from the present state toward the equilibrium s ion, this case, the reaclion rate is beside the ques For instance, considering the reaction 200 7 CO, + C at 600°C which (1-12}, when the present state is the cocxis- is the din eq. was already discu: tence of solid carbon with gas contuining 25% CO and 75% CO2, that 1, affinity is considered to be zero because Lhe state of point m in Fig.? 86 (koe) Fig.2-1 Relation between affinity (ac) and gas compositions 4 for reaction 2CO=CO2+¢ at 1 atm % COrenction should notproceed any more. But, when only CO gas is held at 600°C, namely point. a in Vig. 1-2, the system has the maximum affinity in the direction of 2C0 > CO, + C. Conversely, the maximum affinity in Lhe direction of CO; + C+ 2CO should be realized at point » in which solid carton is coexisting with CO» gus. As you know, after various discussions and trials, it came to be established thut affinity should be expressed by free energy change. shall we discuss a little more of this quantity and its relation with other quantities which are familiar with us The Second Law of Thermodynamics ropy IL is also not necessary to explain to you what the Second law of Thermodynamics is. A part of the eneray of a substance may be converted inlo work, but even under idesi conditions available energy is always limited, and gone part of energy is bounded with the system, The maximum available energy under ideal condition (under reversible change) corresponds (0 so-called froc cnergy, while remaining part of energy is namcd bound energy. Encray is often expressed by the product of a potontiel factor (inten= ve factor} and a quanlity factor (extensive faclor), for example, elec- econd. trical cnergy (watl-seconds) is made up of volls and ampere Considering the thermal cnergy in the same way, which is corresponding to bound energy, the quantity factor S is called entropy, while the potential factor in temperature in ubyolute scale. A given body of matter has associated with it « definite quantity of entropy, which depends upon Lhe kind amount of matter and its temperatures and the bound energy for this system is expressed with TS. Al. a trans— formation or melting point, if Q_ cal of heat is absorbed at T°K, the inerease in Une entropy is expr s case the ned as follows, because in th change is reversible ond isothernal. oss a/ 7 (a1) it is considered to be originated in randomness within substance that thermal cuergy can nol change completely into work but remain sone part Wounded form. Accordingly, entropy can be considered to he meanure for randomiens of the system. The increase in entropy accompanying melting attributed to the increase in randomness caused by breaking of lattice.ub ‘The entropy of 4 substance increages with temperature at a rate depending upon its heat capacity. At constant pressure this is given by the equation: (as / dt) =e, / 3 (2-2) Integrating this, S= 80+ (7-3) where, So corresponds to entropy at O°K, being known zero for every pure crystelline substance depending on the third law of thermodynamics, Thus, when the molar heat capacity ix known at all temperatures down to °K, it is possible to obtain molar entropy at TSK, For a liguid or gascous sub- stance, the values of G/T for melting and boiling must be added. So called standard entropy, Szee, is derived as like this, and some of them are tabu- ated in Yeble 2-1, Using Unis data, we can calculate the entropy at °K. Yable 2-1 Standard entropies cubsteace | Sim | wvetance | Sm | cineteoe | sim | eabotocn | ue, [EEPES Taare wero | TR fee | ae arlewe | i] mom ke moe [ary cena | sz] mow | 29 Bmscl | a4 | Gaon | rovg | me mo | anf ere. a7] meses | ats Roecy | 20 | Gace tal eae | as m0 aime | 98 mee | se) sao | te Mot aels@ | as Mewes ae | Sr | ae feo | Rs | coy ralsom | as Be” TP coc selmo | Bs Be Lal Feo Ha | Seo | ma mip | an rome ai|aw” | ‘cr me | mea | pote | mn Bo | et) sca | am conte | Bi) sm |e cee | em Sore | BS co Rel me | om on fe) Bu) mara | a0 ch | ew! vet won| Teuce | st cos) | Rat’ Fewte) To. or Gio | Bk) est ve |e cow vo 738 cso | mae fiw | ast CaCOr ts) | m2 | MTC what | Naat (o> Ven 8D ube came | esi mow | mel smseo wa | Shie jaee| Mowe | ii] seo wor | em uo A | tose Noewo geo | cas i | ew No how | a5 Gre | Ral ma | ae | Nee new | as Ga | ee] mene |e ow mao) | 23 Go [asinw@. | sul re no cs@ furpam larfre Bono ~20-ssee st Ba 2 n= Sasa tL Bae (24h) jx3_ Free Energy When the bound energy is subtracted trom the total cnergy, the rc- mainder was first eslled free cnorgy by Helmholts. ‘his is the portion of the total cneray wheih, at a constant temperature, in available for producing useful work such as carrying on a chemical reaction. Absolute values of Cree energy are also unknown, but only the changes in free energy are of interest, For metallurgists, the total energy in constant-pressure process, Il, is more conventient than E so energy at constant pressure, ¢, which was firs t defined by Gibbs, is used principally. G = HTS (2-5) ‘Men, in any chemicsl reaction at constant temperature, AC = Al - Tas (2-6) ‘he quantity 2G is the measure of the driving force of a reaction occuring ut fixed temperature and pressure, corresponding to so called affinity. When aG has a negative value, the reaction tends to occur, and the larger the negative value of AG, the greater is the tendency. When a0 is positive Uhe reaction does not occur of its ow accord, but the reverse of back-ward reaction may occur, A zero value of AG is characteristic of chemical equilibrium in the reaction, which mesns that the reaction no longer has s tendency to go in either direction. rom eq. (2-6), so-called Gibbs-Helmiolts' equation is derived. ag = a+ (28) (7) and moreover, a{aG /T) __ a (2-8) Combining with (1-11), AG = aH, - aw? lat - 1/2apt? + 1/enex? + IP (2-9) Thus, when integral conslant T ix deLermined by aG velue at @ definite temperature, ve can derive the change of AG on temperature based upon the heat capacily or heat content equation.Jch_Relation between Free Knergy and Equilibrium Constant Shall we simply derive the relation belween free energy and equiliprium constant, although you can find similar procedure in any textbook. Free energy chunge depending on pressure for 1 mole gay A is expressed as follows: aG = RE d InP, (2-10) By integration, GeRY im +2 (e211) Where I is integral constant. When the gas exints in standard state of 1 atmosphere, the free enerry is called standard free energy and expressed by G°, that is, G = 0° G = 6° + RTnP, (2-12) I, uence, in general, next, ench one mole of gan A and B having prossure Pf and Pi, respectively, react each other un produce cach one mole of gas C und D representing pressure P¢ and Pz, respectively. what is, A+B=c4#D (2-13) Combining the equations corresponding to eq. (2-12), pa AG = go? + Rtn SO (2-14) ACB When the reaction reach equilibrium stale, and represont equilibrium pressures Py, Py, Py and Bp, respectively, PoP oe = warin GSP = -prink = -1.5751 1ogK (7-15) aE because gG= 0. Where K is equilibrium constant, Although Lhe gas phase reaction is used for explanation, the relation of (2-15) is also valid for condensed phase of activity is used instead of partial pressure. Iu is important to understand that the derivation of above equation has involved two essenti#l reletions: (1] G = 0 for the equilibrium state, ana (2) the partial pressure or the activity of cach substence is unity in iti ‘tandard state. 40° is enlled the change of standard free energy, and cxpress the increase in free energy in a hypothetical reaction in which each reactant ix present in its standard state and cach product is formed in its standard state. Of course aG° value does not correspond to equilibrium state, but to standard state, and although aG = 0 at equilibrium state, Pli-46° in not zero in genoral, When the eq. (2-13) is heterogencous reaction in which B and D are pure solid substances and A and C are gus, the term of condensed phase of pure substance can be neglected from the equation as the tollowing cxample: 200 = CO, + ¢ ag? “ROK, ST5P 108 Puy, /Peg Calculation of Chenge of Free Unerey IIs2-1_Vroe Energy Equation Using the eq. (7-6) or (2-9) for the substances in standard state, we got standard free energy change, aG° . aU° can be derived not only trom thermal data as like entropy, heat capacity or heat content, but also be equilibrium constant depending on eq. (2-15), and moreover from electro chemical data as will be mentioned later on, Recently, AG° data have been arranged fairly well for high temperature range in which tne interests of metallurgists arc focussed minly. In the compilation of these data, divtinguished services ere brought by U.S, Burean of Mines dirceted by K.K.Kelley.2) Richardson and Joffes?), Kellogg?) and Kubaschewskii*) are algo publishing valuable data. he style of eq, (2-9) is most precise to express temperature de- 4 from Unis pendence of 46° data, and 4H, aS and gC, are also de equation. But in practical calculations this form is topcomplicated to obtain results, so the following simplified equations are often employed. AG° = A+ BT log T+ CP (2-16) AC? = A+ BP (2-17) The form of (7-16) is adopted by Kubaschowskii et al. lq. (2-17) linear form and is quite simple in calculation. Moreover, the difference of numerical value between (2-17) and (?-9) is not so large in general, for example, the differcnee is only + 600 eal for oxide, which is negligible in practical calculations in comparison with the precision of 2G° deta itself. Although there are some exceptional cases, for cxample, some data for halogen compounds, I'd like to recommend you to usc the data in (2-17) form in general use, AG data for oxide and sulfide ere summarized in Yuble ?-2 and 2-3, respectively. The data in able 2-2 are -25-Tavle 2-2 Stantara free energy change cf fersation of oxide, 40g = 4 + ST (catfnol O:) « 5 * WAG) $02 &) = ALO © UAE) + Os @ = RAMOS G) EBSD (4,5 408 Ce) = HSm08 > {85} ~Or G) = 218h0s Csice) Ore) = WHO 4858) OX) = 2580) Si) Ox) © 295Im04.0) danas) 4040) = EBANOL) Ad.Axe) + Ora) = SBAWOKD Mane) FOK1) = WAOWE Anda) +0x) = 9A EAR) FOE) ~ BS ARO asta) + Ox) = 25 AuO1) aes) + OxR) = 2W08) enai) ~ Oued = 28408) x ats) + One) = £ BeOS) Epa + O48) = 20 MAM) HOARD = EIMAOE EK +Ox@ = EOE x eh; ~ 0x8 = 28 OAC LORS) FOxC@) = EDDY 4018s) 4 Ogg) = BE MOKD 2Cdis) — Org = 22050) BGs) FOng) = ECAR) 2086) + Onl) = 280.3) Beis) FOx8) = 260059) 26x) + O56) = 2206) Beate) +Onle) = £00088) 26.8) 4 Oxe, © 2000R) i} + Ose) = COxe? Ox) = HCHO (20) + Oe) = ICDA 2Cae.s 0 +DKe: = 26 ) + Ong? # Baad Aig) +Oew) = KHOA wert9e See) + Oni) = SeOae |B wo Be POxe) = SOK) Wow 85 ‘Set Owe) = SOs) x ape Waseuce: +O) = See) x naam 28a) + 0¥u) = 2508) x aise 25: tOn@) = 2500) wane Ska) +01) » SOx: Sk +0400 = SiOx } Asis) + Oa) = FA) AND HOAs) = FN) x tNsa eOnu) s2NaiKed x Sie) t Owe) = 2808) * BESa) + Oxo)» $010) Las rOxC@) = 25000 ein) Ox) TeOHe) xb + 0x) = Troi 1 Tal) + Oke) = TeOwt x Sia) + Ox) = SOx) SKI) + OK) = Buus) Sul) OMG) © Se) Tea) #Onies = Tome) Kp) + One) = KOK)Fisk = Woe Geet) Oe» Oats) rte) Once) = IDC Heike) rOxks) = SUK) > aGaD Os) © HVAC hea) +0ne) = 22000) Enh) pas = 2zHK ni) 4 Oxi) = 270000) “2x(0} #0458) = 1100) 23) = Og) = BO BAG 4 ORR) = LOAD an ne au au eur io ae fs | =a | eu | game wena dgple 22 Staréard free energy change of formation of suifiées, Ac ” s x eas tees, aoe Bae A+ BD {eel/aot 82) Senet co [= | Beat Beer Bim HLS keno one pare) x 6 a TGu i +B = Fas (HD Mee Se = 2S, We (ay Be = 2 PWS" e) 4 FEE 2Fes (e482 = 2S Die (a) +S = BFES Co) Eve Go) v8 © BES GS B¥e G) 48 = 208 2FeG) +5 = 2S Ba (a) $8 = 18 6 2h) 0) + ons) 2¥) +85 = 2088 0) 2M Go be = EMS (OD PMs © +55 = E365 () Bhs Ge) + Se = 2MYS GD 2M (0) 45) = 20065 @) ama (9) 48s = EOS (0) 2M (9) $5e = EMS Go) AM) P5136 @) 2Ma cD + Se 2a) 2htu (Dy $82 = 2MS 0) ile cD) F5a = 2185 ily (u) 482 = 2166 6) Mu) Bu > Ma (0) BNL Go) 5a = NaS 2108) B= EUS Bt Go) #84 == 2S" R@ r= SO Aan 0) #59 = Ake AAG G) +84 = Ehes 1Ag (=) +84 = 2888 Aaa) 54 = 143 ANG Go) 434 = 25 6) ANS) 482 2NeS 6) 48 Ge) 15 = 2S 6) ARS Ga) 181 9 BN CD B8eG) Sr a 288 f= 28h) Bee i Seo ase sn 38@) Was 0 Wie 20h G) Fa © 82H.) Bn) 484 = 228 2am 15a = HS C) * *:S02i@ solution anes C0 ae a0 00 own femtso aman yen ta mewn anise 3 hs raasAo Be co mrss were ows Bene issiee iaeia0 ect isi ineiao anit anit emisbaued mainly on the report by Coughlin, and those in Table 2-3 by Richardson et al.?) The precision of most dala is + 3 keal, but data marked with x are not so precise, and smoctimes beyond + 10 Keal. Let me explain a few examples of calculation, Shall we discuss Boudouard'y reaction which has been often quoted in ny Lecture hitherto. aco = Coat ¢ (1-12) We can calculate the change of affinity at 600°C with gan follows. AG = a0? + RE inP5 / Po? composition, a Using Wable 2-1, 40° for (1-12) is calculated, C+ 1/20, = co aG® = ~26760 - 20,987 C+ 0, = CO, aG° = -94260 - 0.277 Thus, 200 = CO, +c AG? = -ho7ko + 41.697 al 600°C, AG = -LoTko + 41,69 x 873 + 4.575 x O73 los Pj, /PeA = -h3ho + a AB? 30 + 3990 Loe Pq, /BG The result is illustrated in Fig.2-1. You can sce nogative value of AG increases with increasing CO peor cent, suggesting increasing affinity of righthand direction of eq, (1-17). When the gas compositions are 25% co and 758002, aG = 0, that in the oystem is in equiibrium state, and iv corresponds to point min Fig.1-2, Although reaction (1-12) can proceed to righthand when the gas contain 25 to 100% CO, if CO % is below 25%, the reaction never proceed to righthand, but proceed to the inverse direction, I suppose you understand the relation or differcnce between ACG and AG? trom this figure. | You should remember that affinity is not expressed by aG®, but by 4G, although in practical calculations the evaluation of AG is not so often «: ried out, because AG® is mainly uscd to derive equili- beium constant by the relation eq. (2-15). In Lhe next place in order to explain the relation between AG? and ‘thermal data, shall we consider about melting of copper. cu(s) = cu(1) (2-18) Nolar heat capacities are, from Table 2-2, Gals) + G, = 9ekt + 1,50¢10S@ cu(l) + ¢, ip 7 750 =28~©, = 2.09 = 1,50+10 8 According to eq. (1-11), OH = AHg + 2,09 T - 0,75+10° 99? From Table 2-?, tne melting point of copper is 135/°K and the heal of fusion is AHiss7 = 3120 cal. Thus, we can determine AHy AH = 1665 + 2.09 T - 0.75410 99 Prom eq. (2-9), AG? = 1665 - 1.81 log B+ 0675-10 8n + Le At 1397°K, aG = aS® =0, because pure solid copper and pure Liquid copper coexist in equilibrium state.(As has already been mentioned, in general ace 26°, but transformation of pure substance is special case.) Anyway, using thie reletion, we can evaluste I, AG? = 1665 - W.81Y log T + 0.75+10°'T? + 12,897 (2-19) At 1000°C and 1100°C, aGfa3 = 190 cal, AGPs75 = -4O cal when pure copper is considered, judging from these results, eq.(2-18) never proceeds to right hand al 1000°C, bul Lo lefLhand, which suggests Uhat solid copper is stable phase, On the contrary, at 1100°C it is suggested that liquid copper is stable. However, these are valid for only pure copper, when copper make alloy with some metal, decrease in melting temperature occurs in general, ana the reaction (?-18) proceeds to righthand even at 100°C. In Fig.?-? phase disgram for Cu-Bi system is illustrated. in this figure, 1000°C corre- sponds to melting point of alMoy P contuining 0.916 mole Cau and 0.08% mole Bi, and et that temperature, melt p is in equilibrium with solid pure copper held at 1000°C, Shall we express the concentrations of Cu(s) and Cul) in eq, (2-18) with a, and ay, respectively. For (2-18), . AG? = -'.575T log K at 1000°C, 190 = -.575 «1273 logas/a, ws log ar/a, -0.034, ay/a, = 0.997 (2-20) 1, thus, At 1000°C, pure solid copper coexist with Viquid alloy P, so, a, 91109,20.2030-40 30,6070 __ 80 go 996 700 600) 300} Temperature (7c) 400] 300) Bi(%) Pig.@-2 Phase diagram for Cu-Bi system a, = 0.927 In summary, pure solid copper can not change into pure liquid copper at 1000°C, but can change into liquid having thermodynamic concentration of 0.997. 1 Variation of fquilibrium Constant with Tomperature From eqs. (2-8) and (2-15), ak (2921) or dink. AML . acyty = OR (ax22) hese are so-called reaction isobar of van't Hoff, showing the variation =30-of equilibrium constant with temperature. Judging from th: equation, i) AF > 0, that is, when the renetion is endothermic, dink/d? > 0, namely, K increase with increasing temperature. ) AH < 0, that is, in exothermic reaction, @Ink,/d? < 0, namely, inereasing temperature results in decrease in K,. This suggests that the cquiliorium shifts to the inverse direction, Unal is, endothermic direction. 4H = 0 results in dink)/ dT = constant, that is, cquilivrium state does not depend on temperature. Roth cases of i) and ii) increasing temperature results in the shift of equilibrium state to endothermic direction, thst is to the direction which prevent increase in Lemperature. These phenomena are explained by the principle of Le Chaterier-Braun, as you know. For example, reaction (1-12), 200 = CO, +c, s exothermic ag has been shown above, i creasing Lempera- ture results in # shift of equilibrium slate Lo Uke inverse direction, as you can see Boudoward's curve results in increasing COZ. As has been already pointed out, variation of AH with temperature is not large in general, especially in narrow temperature range we can assume ib is constant valuc. Integrating eq. (?-??) under this condition, AH pep inx=-M +c (2-83) or dog k= - Ep eet (2-2) ‘These suggests that linear relation is expected between log K and 1/T, and AH will be derived by inclination, Ey. (2-2) is often used for evalua~ tion of experimental results. For example, FeCl, + Hz = Pe + 2HC1 FBGHO Yay Ls) . =17) rog K = DO + 10 Ths, 31-Free Energy - Vompersture Diagram To evaluate the equilibrium state precisely, free encrgy equations avo omployed in goueral, but troe eneray-tomporature diagrams are eometimen vory convenient in order to grasp Une gencrel tendency. The figures for oxides, sulfides and chlorides are given in Wig.2-3, 2-4 and 2-5, re specilively. Moreover, in Fig.2-6 the date of just a fow compounds nre illustrated for explanation. As has becn already mentioned, Une relation is considered to be linear form, und inclination of the lines (dAG /d?) represent. entropy change (45), and moreover, extrapolated values et 0°K show approximile value of AU°, Transition points of participants, for example, transfor- mation points, melting poiate and boiling points, are represented in the figure vith signs T, M, Bctc. AL these temperature, you can see knick corresponding to entropy change (Miq/ 7). The compound described in lower position in more stable in goncral, because it has larger absolute valuc of aG°. For cxample, Cu20 and PbO inl easily. Accordingly, 5 under week reducing atmosphere, 9 stable than FeO, being reduced into are le these metals can be obtained from oxid: while at that time iron is removable into slag in the state of oxide. the next place, using Fig.2-6, shell we discuss the stabilitics of NnO and NiO st 1000%C from the stand points of (a) dissociation pressure of oxygen, (b) reducibility ty Hz ges, (c) reducibility of CO gas. (a) Dissociation pressure of oxygen, P,, 2Me + 0, = 2Me0 (2-25) ag? = “RD lnk" = RT inp, (2-76) This is of course ordinate value of Fig.6-3 and 6-6, end the form of 46° = RI Inpy, is called oxygen potential in gerneral. From the figures, MeO t AGs 59, = RE dn po, = 4.575 x 1273 x low Po, -140 kewl (a) a7 + Pop= 10 724 atm NiO 9G%)75 = -5T koal (B) ste Pg = 2% 1072 atm As a matter of fact, these values can be estimated from the 3Adiigcl, B+ Sigal C4 hg eal, D L>10ie cal Melting point: M(Rleseat) (6) (Orie) Beiding point | B (Hien ® Sabhionlica poine {8 (FLexent) (8) (oxide) a eanssoreation point T (owent) (1) (Casas @y) Reducibility by hyarogen. ing the following equation with (2-25), 84 keal (2-27) Com 20 26°77 Blin + O2 reduction reaction by hydrogen is obteined. Neo + Hy = Me + H,0 (2-28)o 2 4 10° = -Reanlay,0/Py, ) 35932 2 : 8 5, 108? MnO: AG°y2732 26 keal, ++ Py,0/Py, 7 2 12 MIO: -AG%y279= “13.5 Keel = 2x 10? ve Puo/Pity These are also obtained if we can use special axis for H,/120 ratio, as is shown in Fig.2 (c) Redueibility by CO gas MeO + CO = Me + CO (2-29) a6? = -FMIn(I¢9,/Pop) YO + Bep,/ Pog = 107° mio =2x 10? * Bep,/Peo ‘These are also obtained directly, using speciel axis for CO/CO2, illustrated in Pig.6-6. Judging from the results obtained for NiO, it is suggested thet redue- tion of it will be easily realized by Hz or CO gas. On Lhe contrary, ro- auction of MnO is quite hopeless.(high purity CO, Ila). Amyway, ag Like Unis, if we prepare special axis for particular re— action, ve can Pind equilibrium value from free energy-temperature diagram, without any calculations, although precise results can not be expected. However, it should be noticed that, in usual, free energy-Lemperaturc diagram represent only (standard) free energy change, Uhat is, participants should be oxisting in standard state where activity is unity. For example, in eq. (2-28) or (2-29), if reduced metal is obteined as solid solution with iron, the above results are fully meaningless. 1) K.K, Kelley : U.S. Bureau of Mines, Bull. No.384(1935)5 No,406, 407 (1937). J.P. Coughlin : Bull, No.582(1954). 2) P.D. Richardson and Jul. Jeffes : J, Iron Steel Inst. 160( 1948), 2615 163(1949), 3973 166(1950), 2135 171(1952), 165. 3) HH. Kellogg : J. Metals 2(1950), 869; 3(1951), 137. Trans. AIME, 230(1964), 1622. 4) 0, Kubaschewski and FL. Evans : Metallurgical Thermochemistry, 19555 0. Kubaschivski anf J.A. Catterall : Thermochemical Data of Alloys, 1956. ~36-