ne METALLURGICAL THERMODYNAMICS. reo) ‘ Koy som =314K 10" = « (e600) «3.14 x 10°98 o Tare] Ths st 2073 K and any oxygen pressure 70, » the individual ratios are fixed by Eqs. (e) and (), combination of (reo) [Xmal 5.856 X 108 3.14X 107 in accordance with Eq. (d). Establishment of equilibrium (¢) requires that the AGT lines for Fe oxidation and Mn oxidation intersect at 2073 K, ie., that AGieynm = 0. For any oxidation M +40, =MO, clockwise rotation of the ‘G-T line (e.g, the line ab in Fig, 13.1) about the point ofits intersection with lhe T= 0K axis, is effected by decreasing the ratio ayio/ay below unity and, conversely, anticlockwise rotation is effected by increasing the ratio ay o/ay above unity. Also, as the equilibrium constant K is a function only of temperature, then at any oxygen pressure, fo, , in the system M-MO-O; at the temperature T, the equilibrium ayy y/ay¢ ratio must be Mo Poy ay P03(€9,T, pure M/pure MO) where Pg, eq.T, pure Mipure, mo) {© that unique oxygen pressure at the temperature 7 required for equilibrium between pure M and pure MO. Thus for any oxygen pressure, Po,» €quilibrium (c) is established when Eqs. (e) and (f) are satisfied. Under these conditions the AG-T lines for Fe oxidation and Mn oxidation intersect at 1800°C. ‘Thus as a result of the ability to vary aj and ay, equilibrium (¢) can be ‘established at any T and any Po,. Ths isin contrat to the situation illustrated fn Figs 104 and 10.5 where f oth meals nd toh oxides are preset in thet pure states, then an equbrim such a (€) could only be achieved at the single [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 419 unique state (unique T and unique po.) given by the: efor the wo pane onan? ny, een fe AC ‘multiphase multicomponent equilibria are discussed in Sec 134.) 13.3. ALTERNATIVE STANDARD STATES Up to this point in the discussion of solu ° mn of solution thermodynanicy, the standard sat of alton comzosnt his en chown tone Se reece its stable state of existence at the temperature of interest. This i called the aouian standard stat, and InP, 13.2 he sand ste Bis located at the point r. ae for he component In the case where, at the temperature of interest, the pure compo: in « pla sate hich fet fm tat of he une Henan Standard state may be more convenient than the Raoultan standard state. Such cases include the solution ofa gas in a solid or liquid solvent or the solution of a solid in a liguid solvent. The Henrian standard state is obtained from consideration of Henrys law, which, strictly being a limiting law obeyed by the solute Bat infinite dilution, is expressed as “ Fate eka 70 where ap is the activity of B in the solution with respect to the Raoultian standard state, and kp is the Henry's law constant at the temperature 7. ‘Alternatively Henrys aw can be written as Hata (036) where 7 (= kp) is the constant activity coefficient which quantifies the fiffernce between Raoultan solution behavior of B and Henrian solution behavior of B. If the solute obeys Henry's law over a finite composition range, then, over this range, ap = AB “The Hensian standard state is obtained by extrapolating the Henry's law line to Xq = 1. This state (the point h in Fig. 13.2) represents pure B in the hypothetical, nonphysical state in which it would exit as a pure component iit obeyed Henry's law over the entice composition range, i.e. if pure it behaved as it does in dilute solution, The activity of B in the Henrian standard state with respect to the Raoultian standard state having unit activity is piven by Eq. (13.6) s os=78 ‘Thus, in Fig. 13.2, if rb is unity, then hb = 7.420 METALLURGICAL THERMODYNAMICS 3 é Flg.13.2, Uustration of the Raoultian, Henrian, and 1 weight Petoent standard states for com: tp Poment B in abinary A-B system. ee . tw B Having defined the Henrian standard state thus, the activity of Bin a solution, with respect to the Henrian standard state having unit activity is given as hy =foXp (3.7) vhere ty = the Henrian activity ‘fy = the Henrian activity coefficient In that composition range over which the solute B obeys Henry's law, fp and the solute exhibits Henrian ideality. The mole fraction of B in an A-B solution is related to its concentration in weight percent by wide BMWs Xb = Gam B/MWp + (100 — a% BMW, are, respectively, the molecular weights of A and B, Thus, Tie dato, ar ‘nate fraction of B is virtually proportional to the weight percentage of B, ie wt% BX MWa Xe "00x MWp a~\ REACTION EqUILI AWITH COMPONENTS IN CONDENSED SOLUTION 421 ait sandra State can be introduced. This is the |_weight percent standand ‘Aaland a we of tis sate eliminates the neceaiy af oven aoe Tne uae, Obtained by chemical analysis, to mole fractions fr the purpose of tmodynamic calculation, it is of particular com wenience for use in metallic ‘al systems containing dilute solutes. This standard state is formally defined as raw) WEB 71S MBO and is located at that point on the Henry's law line which corresponds to a concentration of 1 weight percent B in A (the point win Fig, 13.2) With respect to the 1 wit standard state having unit activity, the activity of B, Aggy is pan acy = Fw (38) Where fayyigy isthe weight percent activity coefficient, and in that compos- tion range over which the solute B obeys Henry's law, fog) 8 Unity, and hence yours = WB which is of considerable practical convenience. From consideration of the similar triangles awe and ahb in Fig. 13.2, the activity of Bin the | wt% standard state with respect to the Henrian standard state having unit activity is ‘we _ ac MW, ib 7 ab ~ TOOMW, and with respect to the Raoultian standard state having unit activity is MW, TOOMWs, ‘The value of the equilibrium constant K for any reaction, being equal to the quotient of the activities of the reactants and products at reaction equilibrium, necessarily depends on the choice of standard states for the reaction compo- nents. Similarly the magnitude of AG? for the reaction depends on the choice of standard states, and hence, in order to convert from the use of one standard state to another, it is necessary that the free energy differences between the various standard states be known. For the change of standard state, Bin te Raoultan standard state) * Bein the Henran standest state)METALLURGICAL THERMODYNAMICS 23Gin the Honsian standard state) ace A = BOR 20) = Chea ~ Fem = RTM sie Rac dar a8) witere both activities are measured on tle same activity scale. On elther the Raoultan or the Henrian scales, 254in tne Hensian sanders 1b » cin the Raoltian standard state) and hence CB ant) = RT I0 7h (39) where 78 is the Heneian activity coefficient at the temperature 7. For the change of standard state, Bin the Henrian standard state) Bin the 1 wis standard state) (869+ 1 wit) = GP, wig) — GPopy = RT In Blin the 1 we standard state) awe ” “4 B(in the Henrian standard state) where aguin both activities are measured on the same activity scale Gin the 1 we standard state) _ we MWA, 7B(in the Henrian standard site) MP” ab” 1OOMWs, and hence n MWa ABH wey = RTI ToonaWe, uo) For the change of state, Raoultian + 1 w1%, combination of Eqs. (13.9) and (13.10) gives, BMW 7 =arin( BETA 13.0 AG het wm) warn a (3.4) ubscript (R) to denote the Raoultian standard state, the subscript H) Lg ee ed aed teas) eee ght perant standard state, consider agun the oxidation of metal M to the axide MO, at the temperature 7 Mcay + O20) = MO2(R) REACTION EQUILIBRIA WITH COMPONENTS INCONDENEED SOLUTION 423 For this equilibrium Gtr ROAR y= ~Ar i 1M ora in ite ost n Which cet my the Henrian standard state for M, then for YS mow coment 1 we Mery + Org) =MOrce) 26a = Ain ACh Ry ie, “RT In Kp =—RT In K,qy—RT 09 Hon 9 AKO; or rin Me = pry 2 4 Fruvo, STB ayeo, + RT Me Thus ou hh (312) hich relates the activity of M in solution with respect to the Raoultian standard state to the activity of M in solution with espect to the Henrian standard state, 8, i the ease of the composition min Fig. 13.2, mn _ mn hb san he eT Similarly if itis convenient to use the 1 we standard state for M, then, for Mc wes) + Or) =MO2R AGE wm) = BGR) — ACHR + 1 win RT 9 Kaa = RT In Kg) —RTn BN “ oe R 100MWy SMO M03, TW soient oe RT Ig MO erin MOF — rig Meee RT In ey wi Mao, auro, TOON, MVsiven 26 Fu ety WO Mr Tees (13:13)tll METALLURGICAL THERMODYNAMICS. at two tome’ 2Sis OF silicon in binary Fe-Si liquid alloys is shown in Fig. 13.3 oo snmPeratures, Asis sen, Si exhibits conslderable negative deviation from welations M188 at Ye; = 0.1 and 1420°C, ag; = 0.00005. In considering dilute lutions Of Si in Fe, there is an advantage (© using either the Henrian standard state oF the 1 wt% in Fe standard state. a the change of standard state from Raoultian to Henrian et the temperature ACR em) = RTI, 5 Xs 1 wile Si = Xgj = 0.02 133, Theses ot "Thomash Soe saci Weiley Publishing Co., Reading, Mast, 1963}) [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 425 and 6 the experimentally determined variation of log 78, with temperature is en 28 att) = BST4ATX 2.30319 78, 119,300 + 7.087 joules Also for the change of standard state from Henrian to 1 wi% in Fe at the temperature 7, MWe Rie wy = RT Toppa, - ssa warn itis 32.67 joules $0, forthe change Sizay > Sica wis in Fe) Get) + 5Gtat wee) ==119,300 = 25.57 joules © Now, given that a liquid Fe-Si alloy is in equlibium with a SiO, satureted Fe0-SiO, melt and an oxygencontaining atmosphere (the significance of ‘i0,,saturation being that asj9, = 1 in the liquid oxide solution), calculate the relationship between the equlibtium weight percentage of Si in the Fe-Si alloy and the oxygen pressure in the gaseous atmosphere. The pertinent equilibrium is Sia win) + O2q) = SiOa4) w Gat wi) For the reaction Siqy + OG) = Si02(0) aii) AG Gin = —952,700 + 2047 joules in the temperature range 1700 to 2000 K. As AG iy involves oxidation of Si in the Raoultian standaed state, calculation of AG requires Knowledge of the free energy difference between Si in the Raoultian standard state and Si in the 1 wtdbin Fe standard state. Ths has been determined to be AGP =-119,300-25.57 joulesf € METALLURGICAL THERMODYNAMICS a gaenet 0 Gy = 86 fuy — AG) =—833,400 + 229.57 joules 4 pre 280: *Sia wayPo, As0si0, = 4, thes: 833,400 4 29. S31aT * 33149 In hsict we%) np, wri an be assumed that, over an inti composition range of Si in Fe, i dibs Henrian behavior, then, in this range, sic. ye) = wt% Si, and hence 833,400 | 299.5 inwieSi=~saraatt ataa~ PO, Tus inorder that the equilibrium weight percentage of Si in the metal phase be 10,po, at 1600°C must be 5.57 X'10- The equilibrium oxygen pressure for any other weight percentage of Si at 1600°Ciis calculated as Po,= The eror incurred in this caleulation by the assumption that hg weg) = WU S over some initial composition range is demonstrated when this caleulation is considered again in Sec. 13.9. Example: The Activity of Carbon in ‘ron-Carbon Alloys Sec, 10.7 it was seem that the equilibrium Cegraphitey + CO2G) = 260%, © ‘on the CO,/CO ratio /hi stn no eta — 174.57 joule -ATInKy P=PcotPco, However, if, at constant T and P, the ‘nixtureis increased above the minimum limit st by the presence of soli carbon, then the activity of carbon (with respect to solid graphite) in the mixture fall below unity, being given, via Eq. (b), as Pcolbco ‘atio in the CO,-CO sas cctgn = He $9" Ke Peo, If such a CO-COs gas mixture is allowed to contact pure iron atthe temperature 7, equilibrium is established when carbon has dissolved in the iron (being transferred from the ges phase) to the extent that the activity of carbon in the iron equals the activity of carbon in the gas mixture. Thus by observing the variation of the equilibrium carbon content of iron with gas composition, the activity-composition relationship of carbon in iron can be obtained. Such an investigation has been conducted by Smith,* whose results at 1000°C are listed in the first three columns of Table 13.1 Carbon has limited solubility in iron and at 1000°C ‘yiron (the austenite phase) is saturated with carbon at 1.5 weight percent C (X¢ = 0.066);i¢e.,a 1.5 wtf C — 98.5 weve Fe alloy isin equilibrium with pure solid graphite, and hence the activity of carbon in the 1.5 wt% C alloy, with respect to solid graphite, is unity at 1000°C. The activity of carbon in an undersaturated alloy is thus calculated as LolPco)in we equiibrating as © (2GolPco;)in equibrium with graphite cK where, from Eq. (), (Ro/Pcog)in eq with solid graphite = Ke From °R.P. Smith, Equilibrium of ironCarbon Alloys with Mixtures of CO-CO, and CH,-Hy, J. Am, Qhem, Soe,METALLURGICAL THERMODYNAMICS ‘ wae] [ow | |e] & | i ‘a0 | aoe? | aus | suas | 30% | 550 | iano ‘Beet | Seas | Sao | tion | Soca | Sox | Thos ‘Osea | nat | tans | 1150 | 36 | sea | tes cco | onsea | toe | taae | Sane | Se3 | i758 as’ | oe | asa | tae | ars | sea | Lass aaa | iia | “too | iass | ome | sro | 19ee a3 | tue | im | iss | 3p | ano | 2256 sss | fase | 315 | dase | Sie | &23 | 220 Sea | to | cosee | os | isse | Suge | S63 | et oa | ea | ous | Str | tess | gare | St | uae ui | 1081 | o4se | 607 | 1738 | 340 | tas | £266 ja | 1206 | oss | 77 | aes | 3267 | ae | Lt 4 uaa] 321 | ose7 | ais | 1952 | 3286 | ace | 13S wo2 | 1462 | 0646 | 939 | 2016 | 3308 | ast | t3sd tout | taee | ‘toes | oso. | dose | 2308 | 4 | 1980 Sha | tart | aes | Ses | 2S | 3309 | | rose tsas_| 1500 | tose | roo | Goya | 2329 | 320 | 1954 GS.» Kotz = 137.8 and from direct measurement at 1000% cbtined Kg ram = 138.6. ‘The activities of C in Fe, calculated from Eq. (c) are listed in column 4 of Tle 13.1, and the acigry-Xo and ac gyvt% C relationships ate shown in Fig, 14a and b respectively, Activities of C in Fe-C alloys, with respect to the Henrian standard state, are calculated as follows. The equilibrium of interest is for which O69 =-RTInKe -RTIn Recalling that he =feXe where fo 1 a8 X¢ > 0K, can be writen as Peo Ka” Feofo%e Peo Poste tensian standazd state) + COr(g) = 260) , Smith [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 429 or vere Xs trmed the “apparent equilibrium conan” (Note that a fg +1 a %o-0, then Ky» Ky a8 Xe 20) « ‘The values of Ki and log K, foreach composition are listed in columns $ and. 6 of Table 13.1. By plotting log Ki against Xq (as in Fig. 13.52) and extrapolating to Xe = 0, the vale of lop Kr obaned a 308 ont 010 007 ot ons te 2cte) 003 002 oot Fig. 13.4. The activites of carbon in iron-catbon alloys with respect to the wraphite standard state, the Henvin stailard sate, and the 1 weight percent arbor in iron standard state at 1000°C. (From R. P. Smith, Equlbrium of ‘tron Carbon Alloys with Méxtures of CO-CO, and CH,-H, 1. Amt. Chem. Soc, (68 (1):1163 1945],)430 ai 10 METALLURGICAL THERMODYNAMICS 1 os os o7 os os w sete) oa oa os 02 os ox y* retwte) —e 02 Thus 4C3.am 8.3144 X 1273 X 2.303 X 3,06 =--74,600 joules As log Ky = log Ky + log fo, the right-hand scale of Fig. 13.5a can be drawn to live the variation of log fc with Xo, Now from Geary + COaqg) = 2C0Gg) AG, ™ >) ‘ 51,440 joules [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 431 ad Cesesany + CO24g) = 200) AGS ams = 74,600 joules the free energy change forthe change of standard state, i obtained as AG* = 51,440 + 74600 joues 3,160 joules Ring =83144X 1273 in 7 ‘Thus 72 = 892; {e., the Henry's law line intersects the Xo = 1 axis at 892.0n, the Reoults law activity scale. The Henzy’s law line thus posses through the point acs) = 0446, Xe = 0.05, and hence can be drawn accordingly in Fig 13.4, The Henrian activity scale is drawn on the righthand edge of Fig 13.44 01. ‘The 1 wiv Cin Fe standard state is now located on the Henry's law line a the composition 1 wt% C. One wife C is equivalent to Xe = 0.045; and thus, in Fig. 13.46, the Henrys law line pases through the point A (@cigr) = 0:4, tC = 1), which corresponds to the point 4 in Fig. 13.4. ‘Altematively the 1 wt% standard state can be determined as follows. The ‘equilibrium of interest is now Ca wesinFe) +CO2G) = 200g) © for which reo Po Poosfca wim — Peorlca way ¥%C The 1 w0% standacd state is defined as fom) > 1 as wW%> 0 and hence asee- ond “spparent equilibrium constant” can be defined as : : Po Kee Koa ws) 70 ORE where, agtin, Ke > K, as wt%C +0, ‘The values of Ki, and log K¢ are listed in columns 7 and 8 of Table 13.1, and plotting log Kz against wi% C (asin Fig, 13.5b) and extrapolating to wt% C = 0 ‘Bives log Ky am = 1.729cy 08 we C o 016 010 08 foie) o.08 nin eor-atbon Fig. 135, (¢) Log Ki and log fc versus the mole fraction of carbo i loys at 1000°C. (6) Log Az And log fy i ¥ersus weight percent carbon in ‘toncarbon alloys at 1000°C. 432 [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 423 G8 1am =—83144 X 1273 X 2.303 x 1.729 =—42,140 joules and s0 for Ce) = Ca weinrey 40° = G2 - ac? =751,440+ 42,140 = 9300 joules EM TOO X MWe =RT In BX 55.85 aside x 1273 ‘Thus 78 = 892, in agreement with the previous derivation. The Variations of gq with both composition and temperature are lustrated by the ioactvty lines in Fig. 13.6. The agg) = | line traces out the variation of ‘the solubility limit of carbon in iron with temperature. The figure also Includes (es the dashed lines) the Gibbs-Duhen calculated activites of Fe in austenite with respect to pure solid iron and, as the dash-dot-ash lines, the Gibbs-Duhem calculated activities of Fe in liquid alloys with respect to the liquid iron standard state. 13.4 THE GI PHASE RULE In Chap. 7 it was found that the number of degrees of freedom available to a ‘oneccomponent system at equilibrium was related to the number of phases present by means of a simple rule. This rule, the Gibbs phase rule, as applied to a one-component system, was easly derived by virtue of the simplicity of represéitation, By means of a pressure-temperature diagram, of the phase relationships occurring in the system. In a multicomponent system, however, the phase relationships cannot be(@si simply represented; and in such systems the phase rule is a powérful tool in the determination of possible equilibria and the restrictions on these equilibria. The general derivation ‘of the phase rule is as follows, Consider a system containing C chemical species, i,j, k,... (none of which enter into chemical reaction with one another), which occur in P phases °M. G. Benz and J. F, Eliott, The Aust stenite Solidus and Revised ron Carbon Diagram, ‘Trans, Met. Soe. AIME, 221:323 (1961).a (METALLURGICAL THERMODYNAMICS if Lil f Fg. 136, The phase diagram of the iconcarbon system showing isoactiity lines. (from M. G. Bene ond J. F. Elliott, The Austenite Solidus and Revised Iron-Carbon Digger, Franz. Met. Soe. ADME, 221:323 [1961).) [As the thermodynamic state of each of the P phases is determined ture, pressure, and composition (where composi 1 composition variables such as mole fractions ‘of the entire system is specified when its ditions that the system be at complete 6, by specification of its temperat tion is expressed in terms of C or weight percentages), then the state AC + 1) variables are fixed. The con {equilibrium are . _ @= 1) equalities of temperature REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 436 Pa=Py=Py=... (P—1) equatin of presure 0) = 246) = a4¢7)=... (PI) equalities ofthe activity of the species Had = 818) = (9 (P— 1) equalities ofthe activity ofthe species / ‘nd so on for each of the C chemical of the sptcies. Thus the total number of ‘equilibrium conditions, given as the number of equations ables peor uations among the variables of (= 1ye +2) ‘The number of degrees of freedom, F, which the equilibrium in the system may have is defined a the maximum number of variables which may be indepen- dently altered in value without disturbing the equilbrium in the system. This ‘number F is obtained as the difference between the total number of variables available to the system and the minimum number of equations among these ‘variables that is required for maintenance ofthe equilibrium; ie, F=PC+1)-(P-1(C +2) eitin? 3.14) Ina gstem of noneacting species, the aumber of species C equals the umber ‘of components in the system. However if some of the species enter into reaction rth one another, such thatthe eqibium ofthe sytem includes a numberof reaction equlibvia-in addition to the phase, temperature, and pressure tauiliba—then the number of equations among the variables which must be Specied is increased by R, the number of such independent rection equilibria uring inthe systems ef the species and j eat to form the species, then the establishment ofthis ection equim eqsres that, in ech ofthe P pes, G+0)=0r which incresses the number of equations among the variables by one. Thus if the system contains N’ species among which there are R independent reaction ‘equilibria, then AW + 1)-(P=1KN+2)-R (W-R)+2-P In order thatthe phase rule, as given by Eq. (13.14), be generally applicable toMETALLURGICAL THERMODYNAMICS, systems, the number of components in the former ‘be determined either as can thus 1, The minimum number of chemical species required to produce the system stegulibsivm a the number of species in the system minus the number of independent eton equilibria among these species consider the system M, MO, and O; in which the reaction equilibrium Mes) + 302(@) = MOG) is esablshed. This system has three phases (the condensed phases M and MO, tad the gaseous oxygen phase) and has two components. The avalfBle variables ame the temperature Zand the total pressure P. As, at equilibrium, the species M sad MO occur in fixed states, ie., M saturated with oxygen and MO saturated with M, the activities of these two species are fixed. Thus the total pressure P qua the sum of the oxygen pressure in the system and the vapor pressures of| the solid phases M and MQ; and as the latter two are fixed at any given temperature, then any variation in P can only be effecied by varying po. From the phase rule, F = C+ 2—P=2+2—3= ji, she system at equibrium tus only one degree bf freedom. Thus either T may be arbitrarily fixed, in which cas the equilibrium constant Kz-and hence po, (eq,7) is fixed; oF P= PO, + (the vapor pressures of M and MO) can be arbitrarily fixed, in which case Ky and hence T is fixed, If an inert gas is added to the system, then P = po, + inert gax + vapor pressures of M and MO, and s0 Po, and Pine gas MAY be independently varied. The addition of the inert gas as the thitd component increases the number of degrees of freedom to two, but this additional degree of freedom ig restricted to variation of Pinert gasi i. in addition to either 7 or Po, being independently variable, inert gas MY be independently varied, Consider the equilibrium Ms) + COa (gy = MOG) + CO) ‘This three-component, three-phase equilibrium has two degrees of freedom which may be selected from 7, P, pco and Pco,- For example, fixing 7 and P niquely fixes po and Pco, v8 — a a REACTION EQUILIBRIAWITH COMPONENTS IN CONDENSED SOLUTION 437 Peo Kr- eg, ™ P= Pco+PC0, ‘This type of equilibrium i illustrated in Figs. 10.17 and 10.18. If the system contains the solid carbide MC, then the three-component four-phase system (M + MO +MC + gas) has one degre of freedom which again can be selected from 7, P, peo, and Pco,. ASR =N— —3=2, the two: independent reaction equilibria can be selected as Me) +C0sq)=MO{y+COgy* ® md Me) +2004) = MC) + C034) @ Fixing 7s Peo rw pc0; Po, and Kray = Peo which uniquely fixes Pco and pco,, and hence P = Po + Pco3- If solid carbon is also present such that the system contains the phases M, MO, MC, C, and gaseous CO and CO;, then the number of independent reaction ‘equilibria is increased by one, eg. the independent equilibria, Mgs) + CO2(@) = MO() + CO) 0 Mga) + 200g) = MC{a) + COa(e) @ and Cy + Oni) = 2COe) «ain ‘cur, and the number of phases present is increased by one. In this case F'= 0 and the system is invariant, occurring at a unique T and unique values of PCO and 7co, In a multiphase, multicomponent system in which several independent reaction equilibria occur, the number of such equilibria can be calculated as follows. First write a chemical equation for the formation of each species present from its constituent elements; .., in the previous example M+40, =MO © M+ ® +40; =CO © C+0;=C0; - @= YY METALLURGICAL THERMODYNAMICS Tren combine Spidered as being mM in such a manner thet thwe elements aot Seaton i hen et the sytem re elma, The relat tbe above System the specie’ Number of independent reaction equilibria R. In the o, "eset present are M, MO, MC 6, CO and CO. Hence, fom 102 =MO-M sad ths in (e) C+Mo~ ; MO-M=cO or c+No=co+M w a@ C+2M0 ~ PMO~2M= C0, or ¢+2M0= CO) +2M 0 and in (6) Meceme © Tras ane independent equitbnia occur, combinations of which produce other equilibria which occurin the system,eg, “= ms MC+2M0= co, +3M (ai) Mc+Mo =co +2M (ii) M +0, =Mo +co o M + 2C0=co, +MC @ © +00;=200 «i When any three of the equilibria (i) to (vil) are established, then the other five ate established, Example 1 sider again the example discussed on p. 416, in which an examination was mate of ne conditions under which « gud Fete soliton an lg Fe0-Ma0 solution can be in equilibrium with an oxygen-containng atmosphere. This is a three-component system (Fe-Mn-O) existing in three phases (neta-oxide-gs) and ene, from the phase re, de elu ba 90 degrees of freedom, which can be ee Ma “in Pa ee Sua species (O2, Fe, Mn, FeO, cnenty ae Me anlopendent rection equ, which can be [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 430, selected as Fe+10,=Fe0 for which x kor me Ser ® sad Mn +30; =Mn0 for which so a Kara Re OT an PB Xun Ph (@ lf Tandpo, are chosen as the independent variables, is xed by Eq (and %in0 _1=Xre0 4 Fin 7 T= Xpe 7 Rn 78 is fixed by Eq, (i). Thus Xpe0 (and hence Xyqo) and Xre (and hence Xn) are fixed, (6) If Tand Xp, are chosen as the independent variables, Xjjn = 1 — Xe is automatically fixed. Yano _ 1 Xreo _Kaw,7%ite Xero Xtc Kiir-Xre is fixed by Eqs, () and (i), which fixes Xpeq (and henes Xyyo), and is fixed by Ea. (9./ aso ew METALLURGICAL THERMODYNAMICS © Mo, ana x } *Fe 878 chosen as the independent variables, from Eq. (i), E00 = Key : XpePb; tea og otto Xya0 = 1 — — _ ‘ = Rey in 8 ep (A) gg (248) aot Consider the equilibria whi which Vi0u. Ys 01 and VOS0, nt strane! the solid stiches phases he a O50 an io = for equilibrium among all three solid phases and (V, 0, and Sean ne Tis system contain four phases nd tre components Care te tiperature the fourghseequbsum sca a cevsherotrno nd Pao Such an equilibrium is said to be univariant. Now consider the various equilibria which can occur between two poner t ate Of the solid phases and the gas phase. There are 204) ~ V30-¢s) S029) ~ 2024s) '2(e) — SOa(g) @ ¥2000~ VOSO4 (5) —SO2(g) —SOs(g) @) 1205 ¢¢) — VOSO4(5) — $024) — S034) © For (a) the pertinent equilibrium is V2Oa(2) + SO3¢g) = Va0s(e) + S02¢@) Ps0, for which Kaa) — see H, Flood and 0 J. Kleppa, Investigations on the Equilbia inthe System V,0,, von, 080" SO, 80,. Am Chem. Soe, 69:998 (1947) » LN REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 441 For 0) the pertinent equbriam is WVOSO«(0) = Vs 0c + 80rq) +8034) for which Ki) =P50,Ps05 and for (¢) the pertinent equilibrium is 2VOSO4(1) = V20a(2) + 280a4¢) for which Ko = Phos In each of (),(@), and (6), = C-+2—P =2 degres of fresdom, which ifTis fixed, leaves one degree of freedom to be chosen from Ps0q. PS0q» Ot P = P30, + P50. IfP is chosen asthe second degree of freedom, then in (a) the values of ps0, and ps0, are fixed by the requirements that _ Psox P=Ps0,*Pso, 4 Kw)“ p59, in ®) the values of ps0, and pso, are fixed by the requirements that P=Pso,+Ps0, and Kio) =Ps0xP805 and in (c) ps0, and po, ar fixed by the requirements that P=ps0,*Pso, amd Po, =Kor ‘The conditions of phase equilibrium can thus be represented on an isothermal diagram, the coordinates of which are ps0, and Ps03: For equilibrium (@), the allowed varation of ps, and Pso, is that 501280, = Key. This variation is shown as the line ‘OA in Fig. 13.7a;,and in the absence of considerations as to the stability of VOSO« , below OA,V.00 is stable with respect to VzOs, and above OA, the reverse is the case. For equilibrium (6), the allowed variation of Pso, and PSO, is that 0,PS0 = K(o This variation is shown asthe line BC in Fig. 13; and in the absence of considerations as to the stability of V20e, above BC, VOSO, is stable with respect to V2Os, and below BC the reverse is the case. Lines OA and 'BC intersect at the point P which thus gives the unique values of ps0, and so (at the particular temperature T) required for the four-phase equilib- For equilibrium (c), pso, is constant, being given as p89, = Keer ‘This isConstant T so, > © Fig. 13,7, (@)The V,0,-V,0,, VOSC,-¥,04, and VOSO,-V, Oy Qullbsia' in $0,-S0, atmospheres at constant temperature. (6) Retions of phase stability of VOSO, ,V,O,,and V0, in $0,-S0, ‘Mmospheres at constant temperature 442 LON az» REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 443. shown as the line DE which passes through P, and in the absence of ‘considerations as 10 the stability of VzOs, above DE,VOSO, is stable with respect to V04,and below DE the reverse isthe case Figure 13.7 thus shows six lines radiating from the point P. As there are three fields of single-phase stability, then three ofthese lines represent stable equilibria, and three represent metastable equilibria, and the problem is now to distinguish between the two types of equilibria. Its a property of such phase diagrams that the lines of metastable and stable equilibria radiate alternatively from a point such as P (se, for example, Figs. 7.10 and 7.13). Thus one set of lines is PO-PB-PE and the other is PD-PCPA. Below the ine OPE, V;Os i stable; above the line BPE, VOSO, is stable; and tothe lft of the line OPB, V2Os is stable. No such similar scheme exists forthe lines DPC, CPA, and APD, and thus the lines PO-PE-PB are the stable equilibrium lines with the equilibrium along PC being, metastable with respect to VzOs, the equilibrium along PA being metastable with respect to VOSO,, and the equilibrium aloag PD being metastable with respect to V2Os. The phase, or stability diagram is thus as shown in Fig. 13.78, Example 3: Phase Equilibria in the System Cu-O-S ‘The solid phases that can exist in this system are metallic Cu the oxides Cuz and CuO, the sulfides CugS and CuS, the sulfate CuSO, and the oxysulfate CuO-CuS0g, and the gas phase is an O,-S; mixture, Just as the fixing of the activity of one component in a binary system fixes the activity of the other component, the fixing of the activities of two of the components of a ternary system fixes the activity of the third component. Thus when the partial pressures of O, and S2 are fixed in the system Cu-O-S, the activity of Cu is fixed, and a definite equilibrium state occurs. Although the simplest choice of variables is po,, ps,, and 7, it is more convenient, for practical reasons, to consider po,» PSO, and T as the variables, Thus two-dimensional representation of the phase stability can be considered, (a) at constant temperature with so, and po, 28 the variables, or (b) at constant po, (or po,) with T and po, (or s0,) a the variables. At fixed values of po, and ps, , ps0, is fixed by the equilibrium 3S: +0, = 80, Application of the phase rule to a three-component system indicates that an equilibrium among five phases has no degrees of freedom. Thus, if a gas phase is alvays present,a AS METALLURGICAL THERMODYNAMICS 1. Four con, rn | Phase at an eS can be in equ shalt 2. Three 1282 invariant gpeyct” An equilibrium with one another and a gat ‘ Three condensed mis hase at an ste PAS can bein equim wi 4 abi 36 in equilibrium with one nother and a as 3. Two condone YY chosen terme lensed nny rig eat can be tr equlleum wih one another and 8 gts 80, ang.” “MOSER temperature and an abitraly chosen value d oltanly chown te bein equim with the gt pst at an P80, "perature and arbitrary chosen vlues of po, and As seven soli ‘equilibria ‘aval ae can exist, there are (7 X 6X S)/(3 X 2) = 35 possible possible equilibria involyin need. Phases and the gas pluse, (7 X 6)/2 = 21 possible equilibria invoint, M° Condensed phases and the gus phate, and seven However, most of the ag rtp ule condensed phase and the gas phase, metastable. four-phase and the 21 three-phase equilibria are Consider’ constr Msvetion of the stability aazam for the system Cu-O-S at 700°C (973 K) usin 8 log ps lg 7 - tentang maa A AG Fax (KI) 2Cues) + 302(—) = Cus Oe) —94 0 Cus) + Z0rGy = Cud yy -6 Gi) Cues) + 382¢@) = CaS) 101 Gi) Cua) + $Saqe) = CaS -37 w 2Cuysy + $82(g) + $02¢) = CuO-CuSOi) 483. @) Cus) + 382xg) +2021) = CuSOse) 4075 w Sig) + O24) = $0214) 23 + (vi) A. The Equilibrium Cu-Cuz0~Gas Phase From Eq, (i), 2Cu + 40; = C20, AG8n, = 94,000 joules 1 =-RTIn a 3 = 8.3144 X 973 X 2.303 log 2? a, [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 445. or log Po, =—I0.1. Thus, at 973 K, the equilibrium Cu-Cu,Q-gae requires ogo, =~10.1, and this equilibrium, which is drawn at line (A)in Fig. 13.84, is independent of pso,. At lower values of po, , Cu is stale relative to Cu,0, and at higher values of po, , Cu, 0 is stable relative to Ca, 8. The Equilibrium Cu-Cu,S-Gas Phose From Eas. (i) and (vi), 2Cu+ $82 =Cu,$ AGIa x =—101,000 joules and 802 =3S2 +0: AG$ax = 293,000 joules summation of which gives 201 +803 = Cup8+0, AGSq x = 192,000 joules Po, arn 2 P30, = 8.3144 X 973 X 2.303 log 2 (way P50, ‘Therefore, log (Po,/ps0,)= 10-31, or log ps0, =l0gpo, + 10.31, which, drawn as line (B) in Fig. 13.84, isthe variation of po, with Pso, required for the equilibcium Cu-Cu,$-ges at 973 K, Above line (B), CupSis stable relative to Cu, and below the line, Cu is stable relative to CusS. ©The Equilitrium Cu,0-Cu,S-Gas Phase Lines (A) and (B) intersect at log po, =—10.1, log pso, = 0-21, which, at 973K, are the values of logpo, and logpso, at which the fourphase equilibrium Cu-Cu;0-Cu,$-gas occurs. The variation of log po, with log Po, requited forthe equilibrium Cu; $-Cuy0-gas must passthrough this point. From Eqs. () and (vii), 2Cu +40, =Cuz0 AGS, = 94,000 joules and Cu$ +0, =2Cu+S0, — AG3q = -192,000 joules summation of which gives CurS +30, = CuO + $0, eer1,0 a 4 ‘io 090, —= “ REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 447. "0380, —- Fig. 13.8 Construction of the ssbilty dagram for the sytem copper-sufur-onygen at more. AG2q = 286,000 joules P50, marin oe EZ 8.3144 X 973 X 2.303 oe (eo 0,“60 NS cgi a ‘Therefore, i» ee P8i-700, 928 ‘ 08250, This is de 3 logpo, ~ 209 rewa required for yet, © (B) in Fig. 13.80 and isthe variation of po, with Pso, CuSOy is stable “BUilibrium Cuso,-CuO-CuSO4-ga8 at 973 K. Above the line, case, Lines (D) gyg SUE €© CuO-CuS04, and below the line the reverse isthe 6.13, log ps0, = 0.97, which is the point af pad @) interact log 9, occurs, ich the four-phase equilibrium Cu 0-CuS0,-CuO-CuSO. gas @ The Equitisrium Cup, 'O-Cu0-CuS0,-Gas Phase rom Eas. (), (9), and (vi, 201+ 30; = Cur0 CuO-Cuso, = 2¢u +45, +40, AG Pp = 483,000 joules 293,000 joules AG$q =~94,000 joules 35: +0, =50, 68a summation of which gves 10-0480, = C10 +0; +503 AG$n = 96,000 joules T In Po, “P80, = 8.3144 X 973 X 2,303 log po, “750, Thus log Po, *Pso, =—5.15, or log ps0, =—log p9, — 5.15. This is drawn as line (G) in Fig. 13.8e and is the variation of po, with pso, required for the equilibrium Cuz 0-CuO-CuSO4-gas at 973 K. Consideration of lines (D), (F), and (G) radiating from their point of intersection indicates that the lines representing stable equilibria are as drawn in Fig, 13.86 H. The Equilibrium Cu,0-Cu0-Ges Phase From Eqs. @)and (i), 2Cu + j0; = Cuz0 AG$n = -94,000 joules 2Cu0 = 2Cu+ 02 AG Fp = 138,000 joules REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED soLUTION 451 summation of which ger 2010 = C120 +40, AGbr = 44,000 joules = RT log ph? 8.3144 X 973 X 2.303 log pt ‘Thus log po, =—4.72. This is drawn as the line (H) in Fig. 13.8¢ and is the ‘oxygen pressure at 973 K required for the equiibsium between Cu, and CuO. ‘At higher oxygen pressures, CuO is stable relative to Cu,0, and at lower oxygen Pressures CuO is stable relative to CuO. Lines (G) and (H) intersect atthe values of log po, and logpso, required for the fourphase equlibrium Cu, 0-Cu0-CuO-CuSOy-fas. 1. The Equillvium Cu0-CuO-CuSOx-Gas Phase From combination of Eqs. i), (0), and (vi, 2Cu0 +40, + $0; = Cu0-CuS0, for which AGBq = —52,000 joules 8.3144 X 973 X 2.308 X log —4 PB P50, Ths log 83 P50, =~2.79 Jo8P0, or 10g Ps0, Which, drawn as tne (1) in Fig. 13.86, is the variation of po, with pso, required for the equllbrium CuO-Cu0-CuSO,-pas at 973 K. The lines radiating from the intersection of (G), (H), and (I) which represent stable equilibria areas shown in Fig. 13.8, 4. The Equilibrium Cu,S-CuS-Gas Phase From Eas. (ii), (v), and (ri), 2CuS + 0; = CaS +50, AGS, = ~320,000 joules Pso, = 8.3144 X 973 X 2.303 log— Gai) Po,METALLURGICAL THERMODYNAMICS 1 This, drawn as 4 "BPS0, =logpo, +1718 108 P50, = 7.23, wr) i Fig. 13,9 Soo pans intersects tne (E) at 19870, =-9.95, is the seg 973 te Mt which the equilbrium Cu,S-Cus~ 2uS +40, = 2 2 = 2080, for which ‘ 46% =—741,000 joules ~18,631 log 6 Thus log 29, = a onynen 28 20, =~9.95, which, des asthe te ip a eg wa sie the tae got the lines radiating from the inteedee of CO, Cy and Eoopete song atin le equn snowing 139 es hee we : ty diagram is as shown in Fig, 139. As is teen, only f posible 35 equilibria involving three condensed pas aal's na place ou stable, and only 11 of the c anda a ahs got ose 21 equilib nang two conse pues The partial pressure of S, is obtained from. Eq, (vii) as PSO, PE Po, or log ps0; =log po, + 15.73 +4 logps, = 18,631 log Lines of constant ps, thus have unit postive slope in Fig, 13.9. Similarly, lines of constant pgo, are obtained from consideration of the equilibrium SO; + 301 = SOs for which AG $y, = —7610 joules. Thus, so, 1610 = 18,631 log so, “PO, or log ps0, = 3 108P0, — 9-41 + 108Ps0, ee A [REACTION EQUILIBRIAYITH COMPONENTS IN CONDENSED SOLUTION 453 4 tea9,—~ Fig. 149. The stability dlgram forthe system copper-sufur-onygen at 700°C. Which shows that lines of constant pso, have a slope of —3. Figure 13.9 isan isothermal section of the threesdimensidnal stability diagram in T-log Pso, 108 Po, space. Consider now a section of the three-dimensional diagram at pgo,= 0.1 atm using log po, and 1/7 as the variables. In Fig, 13.9 itis seen that, with 0.1 atm, five equilibria involving two condensed phases and a gas phase occur at 973 K, namely CuSOq~CuO-CuSO,-gas at a, CuO-CuSO,-CuO-gas at », CuO-Cuz0-gas at ¢, Cuz0-Cu at d, and Cu-Cu,S-gas ate, The standard free energies of interest are CuO-CuS0, + $0, +403 = 2CuS04 304,370 +2727 joules @« WW METALLURGICAL THERMODYNAMICS : 2 i ‘CHO + £03 +805 = Cu0-CuS04 ' AG° = —305,290 + 2607 joules ) 2010 = 0140 +405 AG° = 139,890 — 98,57 joules © 20u +40, =cy0 AG? = —166,840 + 74.77 joules © 20u +50; =0, +048 AG° = 230,670 — 40.67 joules © 1 For equilibrium (a, logPso, of} = -=304.370_,__272 80 #8; 53144 x 2.3097 * 53144 X 2.303 which, with log ps0, =—1, gives oppo, = 731190 og po, =P? + 304 «@) This is drawn as line A in Fig. 13.104, Above the line CuSO, is stable relative to CuO-CuSO4, and below the line CuO-CuSO, is stable relative to CuSO,. The | point @ on line A in Fig, 13.100 corresponds tothe point ain Fig. 13.9. | | Forequiibrium (), | log pso, Pb; = which, with log pso, =I, gives j log 0, ® “This is drawn as line Bin Fig. 13.102, Above line B CuO-CuSOs i sable eative ‘to CuO, and below the line ‘the reverse is the case, The point 6 in Fig, 13.100 corresponds to the point b in Fig. 13.9. . For equilibrium (c), . togpo, == 2+ 10.29 © ig. 13.10 Construction of the log po, vs. 1/T diagram forthe sytem copper-sulfur- oxygen at go, = 0.1 atm. "i 455400 METALLURGICAL THERMODYNAMICS Which fe a 420, and eto), 13.108 a ne C, Above hi ne CuO i stable ela to in Fig. 13.109 con® Une Cuz0 fe stable relative to CuO. The point ¢on line C UT= 1.09 x yg-5°SPORGE to the point in Fig, 13.9. Lines B and C intersect at the atte oft gu OL® Ks logo, = 5.63 which Wilh P50, 0.1 a, OS ae a Ep co ee cu 200: +50, = cudscusa, ggt=t45, 180-4 35057 joule oO for which 2 + 1872 980,250, = oF with log ps0, = los po, = 23259 + 19.22 ®) cuits drawn as line F in Fig. 13.108 and represents the equlbrium between C220, Cu0-CuS0,, andthe fas phase, The nwt temper at whigh C10 has.a stable existence with pgo, = 0.1 tm is thus 918 K. Lines A and Fintenect at 177 = 128 X 10 (= 600 8, ego, = 2.36, which, with pso, =0.1 atm, is the state of the equilibrium Cu80,-CuO- CuSO,~Cu, O-gas. This is also the minimum temperature at which CuO-CuSO, has a stable existence with pgo, = 0.1 atm. Combination of Eqs (2) and (F) 0 eliminate CuO-CuSO, gives” ©u;0+ 280, +20) =2CuS04 AG = 749,540 + 630.57 jouls @ from which, log Po, 28 = 242.9 or, with log ps0, =—Is logpo, ==262%5+23.26 © ‘This is drawn as line G in Fig, 13.10¢, Above this line CuSO, is stable relative to CuO-CuSOs, and below the line the reverse i the case. [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 457 For equilibrium (4), antes oppo, ==Y825 + 159 » ‘Thi is drawn as line D in Fig 13.10d and the point don this line corresponds to the point d in Fig. 13.9, Above this line CuO is stable relative 1 Cu, and below the line Cui stable relative to Cu,0. For equilibrium (e) ‘which, with log p50, = —1 gives =non topo, = 222132 © ‘Tais is drawn as line Bin Fig. 13.10d and the point eon this lin corresponds to the point ¢ in Fig. 13.9. Above the line Cu is stable relative to CuS, and below the line Cu$ is stable relative to Cu. Lines D and E intersect at 1/7 = 1.24% 10"? (= 805 K), log po, =—13.84, which, with pgo, = 0.1 atm, isthe lowest, ‘temperature at which metallic Cu can exist. Combination of Eqs. (4) and (¢) to eliminate Cu gives Cus +20,=S0; +00 AG =-397,510+ 11537 joules) 20,159 Thus, log = + 6 apg, Ft 602 or, with log ps0, = ® logo, This is drawn as line H in Fig. 13.10¢ Lines G and Hi intersect at IT = 1.16 X 10"? (T= 615 K), log po, = —19.13, whichis thus the minimum ‘temperature at which CuO can exist with pgo, =0.1 atm, ‘Combination of Eqs. (g) and (h) to eliminate Cu,0 gives, Ou$ +80, +30, =2CuS0, AG? = ~1,147,050 + 745.87 joules-2 =10 loapo, —12 -18 -» wa 1ST 1x40 ; spe fields of phase stability in the system coppersulfur-axygen with Pgo, = Fig 13.11 7 » out atm. 458 [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 459 With log ps0, =I this ies = + 1332 orp0, == ‘which is drawn es Une I in Fig. 13.10f. The complete stability diagram with so, =0.1 atm is thus 3s shown in Fig. 13.11. 135. BINARY SYSTEMS INVOLVING COMPOUND FORMATION ‘The phase relationships in a two-component system can be represented on an isobaric temperature-composition phase diagram. Such diagrams are the binary phase diagrams normally encountered in metallurgy. If the two components enter into chemical reaction with one another to form new species, ¢.. ‘compounds, then, in such systems, chemical reaction equilibria and phase equilibria are synonymous. Consider the binary system A-B, the phase diagram of which is shown in Fig. 13.12. In the solid state the negative departures from ideality are suficiently great that compound formation occurs, with there being negligible solubility of ‘Ain B, or Bin A, and negligible range of nonstoichiometry of the compounds ‘ABs, AB, and AB. The system contains the three equilibria 3A+B=A,B A+B=AB A+3B=ABy Liquid solutions a E Fl oa AB Ae ap [48+ aa, ser, % aB+e Ny a AB AB A, 8 Fig. 1312 The phase dlagam for the system A-B in which sre formed thre stoichiometric compounds,m METALLURGICAL THERMODYNAMICS, Yom | ans at AGM = AGH = —4900 joules. Thu, in equilbrated UC + U, at 1750 K, ie AGH = RT inay = 89,100 joules « ay =2:19X 10 (logay = 2.66) Ge = RT Inac =—4900 joules o a¢ = 0.714 (og ag =-0.15) Asa check, with Xe AGM =8.3144.X 175005 In 2.19 X 10 +05 In 0.714) = 47,000 joules, in agreement with Eq, (a) 6, and, with Xe GM = 8.3144 1750 (0.4 In 2.19 X 10 +06 1n0.714) 38,580 joules, in agreement with Eq. (¢) Between the compositions UsC, and UC, the equation of the variation of 4G" with composition is obtained from 38,580 joules at X¢=0.6 32,280 joules at X, s AGM = 94,500%¢ —95,280 joules This line intersects the X¢ =O axis at ~95,280 joules, and the Xc=1 axis at ~180 joules. Thus, aGlf = RTIn ay =-95,280 joules ay = 149 X 10 (opay =-284) AGH = RTIn ac =~780 joules ac = 0.948 (logac = -0.023) [REACTION EQUILIBRIA WITH COMPONENTS INCONDENSED SOLUTION 473. ‘Thus, in UsCs, the activity of uranium can vary ftom 0.00219 to 0.00143 and the activity of carbon can vary, correspondingly, from 0.714 to 0.948, as the state of U;Cy is varied from that of being in equilibrium with UC to that of ‘being in equilibrium with UC. Between the compositions UC, and C, the variation of AG™ with composition is AGM = 96,840X¢ — 96,840 joules ‘Thus, in equilibrated UC, + Cat 1750 K, AG4f = Rr inay ~-96,840 joules or ‘ay = 1.29 X 10° (log ay = 2.89) and ACY =RTinag=0 or ac In UC; the activity of uranium varies from 0.00143 to 0.00129 and the activity of carbon varies from 0.948 to 1 as the state of the UCa varies from that in equilibrium with U,Cs to saturation with carbon. The variations of log ay and log ac with composition are shown in Fig, 13.19. 13.6 THE SOLUBILITY OF GASES IN METALS If ft is considered that the diatomic gas Xz dissolves in the metal M to form. ‘molecules in solution, the appropriate equilibrium would be written as Xa) UE] (a mead © (On the other hand, if itis considered that the gas dissolves to form atoms in solution, the equilibrium would be written as $Xau) = U1 Gn meu ©) where, in both cases, the square brackets denote solution in the metal phase. For equilibrium (a), Ux) ue) Dy, and for equilibrium (6),METALLURGICAL THERMODYNAMICS ' i 2 F a § ! i -2 -3 00204 os 08 30 - xe ¢ Fig 1419. The scdvitis of uranium an Fig 1319, of oranium and carbon in he system U-C bx] Kno) (3.15) Pry If the dissolved gas is sufficiently dilute that it obeys Henrys lw, then x lone] 1 waa) = Dy and wi. Ki wtso) - W841 (13.16) Pky solves atomically or molecularly can be ascertained ‘mining whether Kg) or K(py is constant. Iti invariably indicating thus that atomic solution occurs and that Whether the gas di experimentally by deter found that Kp) is constant, aN - alilies: q REACTION EQUILIGRIA WITH COMPONENTS IN CONDENSED SOLUTION 475 (©) isthe correct expression for the equibrim. Equation (13.18) and (13.16) sg cxreonyof Stet ay, andi he tes been when Twigs is obtained asthe solubility of the gus in weight percent undet a pressure at the temperature of interest. For the solubility of Nin gid ion at 11606°C, Pehlke and Elliot® obtained the variation of wi%6N; with PY? shown in Fig. 13.20 from which itis sen that for . Pag) = Na wesinrs, Kuan (i= 0.045. Variation of the solubility of the gas under a presure of *R, Pehlke and J. F, Eliot, SoWbilty of Nitrogen in Liquid Iron Aloys, ‘Thermodynamics, rant Met, Soe. AIME, 2181088 (1960). 0.050 cons 040 Wight percent 00204 06 08 10 vy, eo Fig 13.20, The solubility of aluogen in iui ron aa function of PRE, at 1606°C. (From R. Pellke and J F, Eliott, Sot of ‘Mrogen in Liquid tron Alloys: J, Thermodynamics, Trans, Met, Soe AIME, 218:1088/1960],~ NT Lam, win snrausunich mrs ts Format pert ° The sofa HO ths shown ERIN of Koy Wi tense and Chipman ? nsf in liquid trom has been studied under a gas of ren “termined livin bby Sherman, Elvander, OWN Pa, g/Py, they vip of lid on Hag + [s] ae for which ) = HS) a Fe eg <2 BeOS) Pe Fea Thscan be tons 7.3. a8. ¥. Gy set Bink Company, Rew York, ns PHAN rh 72. Hew W. Sherman, H. 1. Elvande ‘Thermodynamic Proper ‘Sulfur in Molten Iron- = Ton 188: mm “ ‘a Moen on Sulr aay rene jong Tamra Pops ot 0.08 0.08 0.03 + ey, wr 0.02 + Nitrogen solu oor °o ‘500 1000 1800, 2000 Tempera," jon ofthe solubility ofitopn in ton under Fie 1221 Te gm of alogen with tempertue (Prom 2. 5 Presse oF lo. Gury, Biya emis of Metal,” irom ‘it Boon Company, New York 1953) aN Fig. 13.21, The varia [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 477 10 9 s 8 3 6 e ° ef ae aint 2% elt é 3 1 2 1 2 3 * Percent elf in mele Fig 1.22, The solbitty of slr In gud ion a 3 function of sulfur pressure. (From C. W. Sherman, H. 1. Elvander, and J. Chipman, Thermo- ‘Gyname Properties of Sulfur in Molton Tron Sulfur Alloys, Trane. AINE, 198:334 1950),) Plas 1 on, iee3) where Ks the “apparent equilibrium constant” which is given 2 KY cet). ‘The nonlinear vation of dissoled weight percent sulfur with Pu,siPm;> shown in Fig. 13.22, indicates that K' is not 4 true constant independent of compositions. (we) 1 nO unity and, at any value of {wt%S}, the value of Ais obtained atthe tangent tothe curve in Fig, 13.22. From the efniton of the I weg standard state, Socumy >} 281% S-+0 the dope of the experimental cure in Fig, 13.22 increases toward the value K as [W195] -+0. The variation of log A” with [wt], a four temperatures, is shown in Fig. 13.23, and extrapolation of these lines to (w1% S] = O gives the value of K for the particular temperature, The variation of log K with temperatute then gives the required thermodynamics of the system i,METALLURGICAL THERMODYNAMICS 2 SRT In K = 41,170 + 27,367 joules Combination of this with the standard free energy forthe reaction HaSy = Haig) + $824) namely AG® = 90,290 — 49.397 joules ives AG® =—131,460 + 22.037 joules for the change of state 3526) = [Sli wesia Fe ie, for the isothermal transfer of $ mole of sulfur gus at 1 atm to a 1 wide solution of sulfur in iron. Using a similar experimental technique, Floridis and Chipman* studied the thermodynamics of oxygen solution in liquid iron by measuring the equiibriam Hag) + 10] 1 wes in Fe) = HO) ‘The variations of [wt%0] with px,o/px, in the gas phase at 1500° and 1600°C 7, , Flocdis and J, Chipman, Activity of Oxygen in Liquid Iron Alloys Trane AINE, 212:549 (1958). —A” ) [REACTION EQUILIBRIA WITH COMPONENTS IN CONDENSED SOLUTION 479 fre shown in Fig. 13.24, The curvature ofthe lines, which is similar to that in Fig. 13.23, indicates that Henry's law is act obeyed, and, again, K for the ‘equilibrium is obtained as the limiting slope of the line as {wt%O] 0. The variation of X with Tin the range 1536°-1700°C gives, AG* =~134,700 + 61.217 joules which, together with . 4G° =—246,000 + $4.87 joules for Taq) +404) = #20) ives AG® = ~111,300~ 6.41 joules for the change of state 20x) = [Ol a wen) ‘The deviations of the full lines from Hensian behavior (indicated by the broken lines) in Fig. 13.26 gives 108 Fo ay “0-20 [1% 0}, a as as| PHO 04 * oa] a2] on 0 01 02 Weight parcent cxygen Fig 1324, The solubility of oxygen in gui ron aba function of Px, of pu, im We gas phase at 150" and 1600"C (Hendan behavior is show as thetbcoke ines).