6 Stability Relationships and Silicate Equilibria Stability relationships among minerals can be thought of in several different ways; the most convenient approaches for understanding natural water systems are summa- rized by the questions: 1. 1s solution A supersaturated, undersaturated, or in equilibrium with mineral B? 2. Which is more stable, mineral B or mineral C, in contact with solution A? 3. Is solution A in equilibrium with mineral B if certain assumptions are made. concerning a component that has not been measured? SOLUBILITY EQUILIBRIA (CONGRUENT SOLUTION) The simplest example of mineral-solution equilibrium would be dissolution of a min- eral such as quartz. At pH values below about 9, this can be represented by the equa- tion SiOrquns + 2H20 = HsSiOnay Key = @vysio, (assuming that ano = 1) = 1 10% at 25°C Any solution (at 25°C) in which anusi, = 1 X 10~* would be in equilibrium with quartz. Solutions with higher ay,sio, Values would be supersaturated, and those with lower values would be undersaturated. Similar relationships hold for amorphous sil- ica, which has a solubility constant of 2 x 107? at 25°C. At high pH values, the solubility equilibrium is slightly more complicated. H,SiO« is an acid just as H2COs is, and at high pH values it dissociates into Hy SiOz and H,SiO3”. The equilibrium constants are100 Stability Relationships and Silicate Equilibria Chap. 6 H,SiO; = H:SiOi + H’ auysionne K= Onusiou = 10°" at 25°C H,SiO7 = H)SiOX + H* Ky = si aa ans03 = 10°" at 25°C The total dissolved silica concentration, (mso;)r, will be the sum of the ionized and un-ionized species: (msio;)r = Munsio, + muysiog + Mx:si02 If activity coefficients are neglected, Ky, KK: (msio.)r rms eote Se :) aw aie ‘The total dissolved sifica concentration in equilibrium with quartz or amorphous sil- ica will thus increase dramatically at high pH values (Fig. 6-1). Note the similarity to the equation (Chapter 4) ty of dissolved slice species Log act 1 af 1 ~ 2 a 6 8 10 2 14 pH Figure 6-1 Activities of dissolved silica species in equilibrium with quartz at 25°C. The heavy line represents the sum of the activities of individual species. The dashed line isthe corresponding sum for equilibrium with amorphous silicaSolubility Equilibria (Congruent Solution? 101 300; = myoo(1 +S 5 £43) where the K values refer to the carbonate system. Ic must be emphasized that although total dissolved silica concentrations may be high in alkaline waters, this does not imply that the activity of H.SiO, is high in those waters, just as a high bicarbonate or carbonate concentration in a water does not imply a high Pco,. At high pH values, polymeric silicate ions (ions containing ‘more than one silicon atom) may also be present in solution, but the presence of these species does not change significantly the solubility relationships. ‘The solubility of a mineral such as brucite [Mg(OH),] can be represented by a solubility product Mg(OH). = Mg’? + 20H- Ko = amerabu (6-1) Since pH is a more convenient variable than aon, Eq. (6-1) can be written instead as Mg(OH): + 2H* = Mg** + 24:0 Kn = OE (6-2) (Keo = Koy/K2, where K, is the dissociation constant of water; Ky = 10"? at 25°C.) Solubility of Magnesium Silicates ‘The solubilities of various magnesium silicates can be presented as more compli- cated solubility products: Mg»SisO,o(OH)2 + 6H* + 4H,O = 3Mg?* + 4H,SiO; tale Keg, = Sabra abe or log Ke = 3 iog(°) + 4 log anusion (6-3) Similarly, for serpentine Mg;Siz0,(OH)s + 6H" = 3Mg?* + 2H,SiO, + HO serpentine + 2 log arsio. (64)Loa By eis 102 Stability Relationships and Silicate Equilibria Chap. 6 and for sepiolite Mg. SigO\s(OH)2 + 6H:0 + 8H* + HzO = 4Mg** + 6HSiOs sepiolite 4 ooah aie afusiog Kepioiite = a ate log Kecpioire = 4 iog(“*#") + 6 log ansio, (6-5) aie ‘These solubility relationships (Eqs. (6-2) to (6-5)} can all be displayed as straight lines on a graph with log (amg+/afi) and log au,sio, as axes (Fig. 6-2). The slopes of the lines are determined by the stoichiometry of the dissolution reaction (i.e., by the Mg/Si ratio in the mineral), and the intercepts by the specific values of the K’s, which are determined from the free energies of formation of the minerals, Only water compositions that plot on a specific line are in equilibrium with a particu- lar phase. Thus a water whose composition plots at point A (Fig. 6-2) is undersatu- rated with respect to all the minerals under consideration. At point B, the water is in equilibrium with talc, but undersaturated with respect to serpentine, sepiolite, quartz, and amorphous silica. At point C, the water is supersaturated with respect to talc and quartz, but undersaturated with respect to sepiolite, amorphous silica, and serpentine. Note that any water composition plotting outside the heavy line sur- $8 $7 — 3 16 3 2) jz 2 Solution 10 Figure 6-2. Solubility relationships in the system MgO-SiO;-H20 at 25°C. Free energies of tale and serpentine from 8 1 ricer et al. ; free energy of sep- w + 5 t =, Bricker etal. (1973) By of sp: jolite from Christ et al. (1973). For ex 09 B,si04 planation of A, B, and C, see textSolubility Equilibria (Congruent Solution) 103 rounding the solution field cannot represent chemical equilibrium, since the water is supersaturated with respect to one or more solid phases. Note also that sepiolite must always be metastable in contact with water at 25°C, because solutions in equilibrium with sepiolite are always supersaturated with respect to one of the other solid phases. Solubility of Gibbsite The solubility of gibbsite [Al(OH)s] is complicated by the fact that dissolved alu- minum can exist in several forms in solution, In the absence of other ligands, the ‘most important are AP'*, A(OH)?*, Al(OH);, Al(QH)S, and AIOH)z. The activ- ity of AP* in equilibrium with gibbsite is given by AIH); + 3H* = AP* + 3120 at (6-6) aie Key At low pH, AP* is the dominant species in solution, and the solubility of gibbsite decreases rapidly as pH increases. As pH increases, however, the relative impor- tance of the hydroxy complexes increases, and their behavior controls the solubility of gibbsite. Formation of the complexes can be described by the equations AL + H20 = AKOH)* + He = Galo aur aq Al? + 2H,O = AKOH)3 + 2H” Kai 2 = Zatowsaier Ka = aan Al* + 3H,0 = Al(OH)$ + 3H* Kay, = Satonntale (6-9) anv AP" + 4H,0 = AKOH)s + 4H" avon sat Kan = (6-10) aap The total dissolved aluminum concentration is the sum of the concentrations of the individual species Maiwout) = Mar + Mayor?* + Mayows + Mayow§ + Mayor; Substituting Equations (6-6) through (6-10) and neglecting activity coefficients gives Kins ay abeStability Relationships and Silicate Equilibria Chap. 6 supersaturated Log activity of di Figure 6-3 Activities of dissolved alu- ‘minum species in equilibrium with gibts- ite (AIOH)s] at 25°C. Heavy line is sum of individual activities. Data from Nord strom et al., 1984, Combining Eqs. (6-11) and (6-6) gives the total concentration of dissolved alu- minum ia equilibrium with gibbsite: Maxson = Kola + Kiwale + Kean + Ka + Kal] (6-12) ‘The activities of each of the species for a solution in equilibrium with gibbsite are shown in Fig, 6-3. Note the following: 1, The solubility of gibbsite is very Jow except at very low and high pH 2. As the pH increases, the complexes containing progressively more hydroxide groups become progressively more important, 3. When cationic species dominate, the solubility of gibbsite decreases with in- creasing pH. When anionic species dontinate, the solubility increases with in- creasing pH. This observation can be generalized to the solubilities of all ox- ides ard hydroxides and of many other solids. ‘Solubil y of Aluminosilicates The behavior of aiuminum makes it impossible to present the solubility of aluminum sificates in as simple a way as was done for magnesium silicates. In principle, a three-dimensional diagram is needed with aluminum concentration, silica activity, and pH as axes, Three-dimensional diagrams can be represented by contours on a two-dimensional diagram. The solubilities of gibbsite, kaolinite [AlSizOs(OH)s), and pyrophyllite [Al,SisO1n(OH)2] at four different silica activities are shown in Fig, 6-4. The aluminum concentration in equilibrium withi gibbsite is independent ofL099. Solubility Equilibria (Congruent Solution) 105 L09 04 Logan 2 4 6 8 7 pH pH ‘) @ igure 6-4 Sum of activities of dissolved aluminum species in equilibrium with gibbsite, kaolinite, and pyrophyllte at different activites of H,SiOs ica activity, as would be expected since gibbsite contains no silicon, but the alu- minum activity in equilibrium with kaolinite and pyrophyllite decreases as silica ac- tivity increases. This can also be shown by plotting the aluminum concentration at the solubility minimum (pH 6.2) for each mineral (Fig. 6-5) An additional problem for most aluminosilicates is that the total dissolved alu- minum concentrations at equilibrium are often extremely low. For typical fresh wa- ters in equilibrium with kaolinite or a smectite, the dissolved aluminum concentra- tions are 0.1 to 1 pg/. It is difficult to measure aluminum concentrations accurately at this level and almost impossible to determine accurately the aluminum species present (organic or fluoride complexes are often important). Uncertainties in the aluminum analyses commonly introduce {arge uncertainties into the solubility calcu- lation.106 Stability Relationships and Silicate Equilibria Chap. 6 Figure 65 Sum of activites of dis- solved aluminum species in equilibrium with gibbsite, kaolinite, and pyrophyllite at pH 6.2 as a function of activity of Lea 24504 H,Si0, in solution INCONGRUENT SOLUTION AND STABILITY DIAGRAMS Because the concentration of dissolved aluminum is usually very small, an alterna tive approach is to assume that aluminum is retained entirely in solid phases and to write reactions between minerals on this basis. This is equivalent to treating Al,Os as an inert component in the sense of Thompson (1955) or to saying that the chemi- cal potential of AlzOs is controlled by reactions in the mineral-water system. An advantage of this approach is that it reduces the number of Variables and allows sta- bility relationships in some four-component systems to be displayed on two-dimen- sional diagrams. When this approach is used, we can no longer consider the precipi- tation-dissolution of a single mineral, but must consider reactions between two minerals. For example, 0.5ALSi,05(OH)s + 2.5H:0 = Al(OH); + H,SiO, kaolinite gibbsite Kusoran = anusice At HySiO, activities above a particular value (about 10~** at 25°C), kaolinite is more stable than gibbsite, and at H,SiO, activities below that value, gibbsite is more stable than kaolinite. It is impossible to say whether or not a particular solution is in equilibrium with kaolinite or gibbsite without knowing the dissolved aluminum con- centration, A similar equation can be written for the kaolinite-pyrophyliite reaction: 0.5Al2SisO10(OH)2 + 2.5H20 = 8.5ALSi20;(OH)s + «SiOx Kpyteot = Quysio, = 1074 at 25°C In this case the equilibrium silica activity (10°?) is greater than the solubility of amorphous silica (10-27), which implies that pyrophyllite is unstable in contact with water at 25°C and | atm,Incongruent Solution and Stability Diagrams 107 itis instructive to compare the results of this approach with Figs. 6-4 and 6-5. Below the silica activity corresponding to Korg». the concentration of Al in equi- librium with gibbsite is less than that in equilibrium with kaolinite, At silica activi- ties above Ku.so, the reverse is true. When the silica activity equals Kyougo, the concentration of aluminum in equilibrium with both phases is identical. A similar set of relationships holds for the pair pyrophyllite~kaolinite at the silica activity corre- sponding to Kpy-sscr In general, at any particular silica activity, the most stable aluminurn hydrox- ide or silicate will be the one with the lowest equilibrium dissolved aluminum con- centration, This can be seen by considering the kaolinite-gibbsite pait in Fig. 6-4(a). Any solution in equilibrium with kaolinite will contain aluminum species at a higher activity than corresponds to equilibrium with gibbsite. That is equivalent to saying that the solution is supersaturated with respect to gibbsite, and there will be a release of free energy if gibbsite precipitates. Conversely, any solution in equi- librium with gibbsite at the HsSiO, activity of Fig. 6-4(a) will be undersaturated with respect to kaolinite, and kaolinite cannot precipitate spontaneously. The same logic applies to all the curves in Fig. 6-4: whenever a solid phase that is more solu- ble (meaning here has a higher equilibrium dissolved Al activity) converts: at con- stant diysio, t0 one that is less soluble, there is a net release of free energy. Equi- librium is the state of minimum free energy, and hence the least soluble phase is the ‘most stable. Another conclusion from Figs. 6-4 and 6-5 is that a solution with any particular silica activity can be in equilibrium with any of the aluminum hydroxides or silicates, provided that the dissolved aluminum activity is appropriate. The equi- librium will be metastable if the solid phase is not the most stable one at that silica activity. A similar approach can be used for minerals containing cations in addition to aluminum and silicon. Consider, for example, reactions between pairs of minerals in the system K,0-AlsO;-SiO,-H:0: 2KALSis0;(OH)2 + 2H* + 3H,0 = 3A1Six0(0H). + 2K* muscovite kaolinite Kyroxach = — (6-14) IKALSiOs + IH" + 9H20 = AlSi04OH), + 2K" + 4H,Si0, K-feldspar kaolinite _ the atasion K. a ake Kena = © alusio. (6-15) ane108 Stability Relationships and Silicate Equilibria Chap. 6 3KAISi;Os + 2H* + 12H20 = KAt:SisOw(OH), + 2K" + 6H.SIO, K-toldspar muscovite = theahason anv Kisomu = = alusiou (6-16) aw KAbSisQ(OH): + H* + 9H20 = 3AI(OH)s + K* + 3H,SiIO, muscovite gibbsite Kme = abssicn (6-17) aw All these equilibrium constant expressions [Eqs. (6—14) through (6-17)| can be displayed as straight lines on a graph with log (ax-/au+) and log an,sio, aS axes (Fig. 6-6). The slopes of the lines are determined by the stoichiometry of the reac tions, and the positions of the lines by the numerical values of the equilibrium con- stants, which are determined from the free energies of formation of the various spe- cies. The free energies used to construct the diagrams in this chapter are shown in ‘Table 6-1. Uncertainties associated with these numbers are discussed at the end of the chapter. ‘The equations listed above and the lines of Fig. 6-6 are only a few of the possi- ble reactions that could have been written among the same set of minerals. For x ample, we did not include the reaction KAISi;Og + H* + 7H2O = AI(OH)s + K* + 3HsSiO, K-feldspar gibbsite ax" Kispan = abysioy ae faye) * \ B 3} Givtae I | Kootnive 2 i i | | 1 ! 1 | Pyro. 1 1 [phyllite ity relationships among L \ «| some minerals in the system K;O- ou 4 ad ~% — AhO)-SiOz-H20 at 25°C.Incongruent Solution and Stability Diagrams 103 TABLE 6-1 FAEE-ENERGY VALUES (kJ/mole) USED IN CONSTRUCTING STABILITY DIAGRAMS. Gibbsite ACOH), Kaolinite AlsSi:0,(019« Pyrophyllite AlSisO (OH) Muscovite KAI Si:0;o(OH)s K-feldspar KAISisOs Albite NaAlSisOs Anateite NaAlSisOe- HO Ne-beidellitet Nao 1A Sip O(OH2 Ca-beideliter Cap. 16-Alz s9SizarOi OW): Laumontite (zeolite) CaAb Sin 44,0 K Nav ca HASiO. #0 = 1st — 3800 = 5215 = 5605 — 3767 = 3715 — 3090 = 5382 ~ 5388 -eml = 283.27 = 261.91 = 553.58 = 13166 = 237.13 "Formulas represent multiples of one-third rather than of 0.330. Loy alae) tt Ginpsite 72 108 auas:04 Figure 6-7 Stabitity relationships among some minerals in the system K;0- Al,Or-SiO,-Hs0 at 25°C, showing the metastable K-feldspar-gibbsite boundary and the metastable extensions of the sta- ble boundaries This boundary is shown as a dashed line in Fig. 6-7. It can be seen by inspection that it must be a metastable boundary; immediately to the right of the dashed line, K-feldspar is unstable with respect to muscovite or kaolinite. If K-feldspar is unstable in that region, any boundary involving K-feldspar cannot be a stable boundary. Simi- larly, gibbsite is not stable immediately to the left of the dashed line, so any boundary involving gibbsite must be metastable. The same logic can be applied to other possible boundaries in the system and to the various possible extensions of the boundaries shown in Fig. 6-7. The significance of the lines and areas in Fig. 6-6 is different from those on Fig. 6-2. In Fig. 6-6, the area kaolinite represents solution compositions in which