Partial Pressure Diagrams At 25°C and | atmosphere total pressure, equilibrium relations for reactions of type 1, solid-solid reacti represent, inasmuch as the mineral temperature and pressure. It is mere chance if the free energy of such a reaction happens to be zero under these arbitrarily chosen conditions. .er hand, reactions of type 2, involving a gas phase of variable pphase is equal to its partial pressure measured in atmosp! all gases behave nearly ideally under these conditions. among fugacity, activity, and pressure have been detail in Chapter 2 STABILITY OF WATER ‘The most fundamental chemi ty of water, If we assume equil ion products hydrogen and oxygen, we can wri 2H,O, = 2H, , + Org. 6.) “The equilibrium constant is a - (62) for neasly pure water (H,O] z 1, and PisPo, = K. 63) “The fre energy relations for equation (6.1) are Fig, + AFjo, ~ 24Fjyyo ~ AF? 4) PARTIAL PRESSURE DIAGRAMS Ms Substituting numerical values and solving 65) mn between standard free energy of reaction and AF; = —1.364 log K . UPPER LIMIT OF m0 STABLITY-Poe« 1 arMosPHeRe PARTIAL. PRESSURES IN EQUILIBRIUM WITH PORE TKO tog Pos - LOWER LMIT_OF HsO STABILITY PHe= | ATMOSPHEREroom temperature is extremé he partial pressure can be used, assuming equilibrium, to characte range of stability of water. If the partial pressure of either hydrogen or oxygen exceeds 1 atmosphere at earth surface conditions, the gas pressure will exceed that of the atmosphere, and oxygen or hydrogen, as the case may be, will bbe released from the water, which will decompose to yield more oxygen ‘or hydrogen, When Po, PA, = 10° When Py, = 1, then Py, = 10-48, (6.7) 19-83 T = 10", (6.8) If an arbitrary value is given to either oxygen or hydrogen partial pressure, the equilibrium is fixed. It is convenient for further reference to make a plot of Py, against Po, so that if either gas pressure is known, the other can be obtained without calculation (Figure 6.1). STABILITY OF IRON OXIDES interest can be handled in the same way. The first step reactions in terms of the iron compounds and gaseous oxygen, being careful to include all permutations and combinations Fe, + 40a _ = FeO, (6.3) SFr, + 202¢ = Feu Fey + 30a = FesOo¢ BFeO, + Ong = FeOce 2FeO, + 10ag = FesOo¢ 2FeO, + 1024 = 3Fes0s.- Because the activities of the erystaline solids are is at equilibrium at a particular partial pressure of oxygen. The calculations necessary are illustrated by solving for Pa, for equilibrium in reaction (6.14) [Fe,0,}* FeO Pry St PARTIAL PRESSURE DIAGRAMS. w The standard free energy of the reaction is IAF irmoy ~ 24Fjrmoy ~ FAP iog = 4F3. (6.16) jumbers 3(- = 2242.4) — 4(0) = AR? AF? = —46.5 keal. (6.17) Then AF? = -1.364 log pts ; 1 46.5 = ~ 1.364 og pre Po, = 10-2 atm. ‘Table results of the calculations for the various equations. Pressure of Oxygen for Equilibrium Becwoen Iron-Oxygen Compounds a 25°C and I Atmosphere Tots Prestre ig at the ‘eceur if th pressures are a useful yas ‘widation experimen8 09/0, compounds rmetarable {in equlibrivm with various Fic. 62. Bar graph showing Dashed lines 265°C and | Smoaphere 0% is metastable because iron converts to magnetite before it goes to FeO. To put it another way, if we write APO, = FesOy 2 + Fey the relation in terms of a solic-soli re ive, and that FeO will disproportionate in mn, we find that ‘There are numerous ways of checking metastable rel of the Po, yardstick is as convenient as most, PARTIAL PRESSURE DIAGRAMS we # Fe20s + 140 , bine Fei0 ore Fede * Fesoue 0) 5 Ho mr 4 Fe Oe+ He 3 43. Composite diagram sho "Cand | mosphere total pr on Figure 64 ipward Po,-wise along the bar graph, it is found that the ‘oceur is from FeyOx to Fe,Og simplified bar graph of the stable phases Fe, FesO,, and FeO, can now be constructed, and the first dividend accruing from use of Po, cancd, for direct comparison can be made with the Po, relations for ure 68). Although a Poy value of 10° peshaps has ficance by itself, comparison with Ie er of water at earth surface conditions, and furthermore, that magnetite ‘ales fr gas prestutes inthe three phage Gl ives the ranges it of water stability. Therefore, of pressures possible for two-phase associations. PPoo DIAGRAMS is stable only under strong reducing condi and is not reduced itself even in the presence of water and hydrogen under 1 atmosphere pressuré Figure 6.3 shows th ree-component composition diagram Fe-Os-Hz. Figure 6.4 shows such a diagram, from Figure 6.3. At the bottom of Figure 6. Fe, + COxg + 40s y = FeCOs. Fey ¢ + 800, 4 = 3FeCOs. + 10a FeiOy¢ + CO, ¢ = BFeCOs + 10a g AF jreco, ~ AF ire ~ AF co, ~ 34F jo, = AFF }) — (=94.26) ~ (0) = - 66.80 kcal, ~ 66.80 = ~ 1,364 log K log K = 49.0 = log ~$log Po, ~ log Poo, = #2 19.0 log Peo, = —49.0 ~ flog Po, ms for reactions (6.21) and (6.22) yield the following Defining Equation in Terms Boundary oto, and Po, FeFeco, 2 Poo, = 49.0 ~ $04 Po, Fe OnFeCe 8 Poo, = 10.3 + 9 FesOnFeCO, coexist, and water is unstable, ‘Thus, this field corresponds to the ti from iron to hydrogen on he field on Figure 6.3 independent of the amount and thi sebse PARTIAL PRESSURE OLAGRAMS 19 1 corresponding value for Pg,, and then draw: int obtained. ns of Figure 6.5, the metastability of the various the diagram can be deduced by In a plot of log Po, vs. log Peo,» the boundaries between these three pairs are straight lines with slopes of —4, +4, and +4, respectively. Figure 6.5 shows these boundaries, plus those for the iran oxides and water. A simple method of plotting is to substitute an arbitrary value HEMATITE Pxoaro re é / Lo 2 i 0 : i = i a [Tae TT ae Pooe Fic. 6.6. Stability relations of some iron compounds a function of Po, and Peo, a€ 25°C Fc. 68. Plot of equations representing stability relation of iron compound a functions tnd afew atmospheres maximum total prersure. Stability relations for water are of Pay and Peo, 825°C. ‘uperimpoted