18.

1 Chapter 18 Solubility and Complex-Ion Equilibria In a saturated solution of a slightly soluble salt, the dissolved solute and undissolved solid are in a dynamic equilibrium. We will look at AgCl as an example: AgCl (s) Ag+ (aq) + Cl! (aq) This is a true heterogeneous equilibrium, provided even the most minute quantity of undissolved AgCl is present. Therefore, we should already know how to write the equilibrium constant expression for this process. K = [Ag+][Cl!] = Ksp where Ksp is referred to as the solubility product constant. recall that AgCl, as a pure solid, is not included in the equilibrium constant expression. We can make generalizations regarding the relationship between [Ag+], [Cl!] and Ksp: 1. When solid AgCl is added to pure water, the solid will dissolve into Ag+ (aq) and Cl! (aq) until [Ag+][Cl!] = Ksp. 2. If an aqueous solution containing Ag+ is added to an aqueous solution containing Cl!, precipitation of AgCl will not occur until [Ag+][Cl!] = Ksp.

The general expression for Ksp comes from the equation describing the dissolution process: MmXx (s) m Mx+(aq) + x Xm! (aq) so Ksp = [Mx+]m [Xm!]x Values of Ksp for several slightly soluble salts are tabulated in Table 17.1 of your text. We can describe the extent of dissolution of a slightly soluble salt in terms of its solubility or molar solubility. Solubility = The mass of solute per liter of a saturated solution. (Solubilities are often expressed in terms of the mass of solute per 100 mL of water.) The distinction between volume of solvent and volume of solution is not very great for solutions of slightly soluble salts, so we can often use volume of solvent and volume of solution interchangeably without introducing serious error.

18.2 Molar solubility = The number of moles of solute in one liter of saturated solution or the molar concentration of solute in a saturated solution.

We can use the molar solubility of a compound to determine its Ksp and vice versa as the next two examples will illustrate. Example: At 25C, the solubility of BaF2 in water is 1.3 g @ L!1. Calculate Ksp for BaF2 at this temperature.

BaF2 (s) [ ]i )[ ] [ ]eq

Ba2+ (aq) + 0 +x 7.4 x 10!3 M

2 F! (aq) 0 +2x 1.48 x 10!2 M

Ksp = [Ba2+][F!]2 = (7.4 x 10!3)(1.48 x 10!2) = 1.7 x 10!6 Example: What is the solubility of Ag3PO4 in water at 25C if its Ksp is 2.8 x 10!18 at this temperature? Ag3PO4 (s) [ ]i )[ ] [ ]eq 3 Ag+ (aq) + 0 +3x 3x PO43! (aq) 0 +x x

For every formula unit of Ag3PO4 that dissolves, we get 3 formula units of Ag+ and 1 formula unit of PO43!. We can therefore equate the solubility of Ag3PO4 with the concentration of PO43! ( = x ) in the saturated solution. Ksp = 2.8 x 10!18 = [Ag+]3[PO43!] = (3x)3(x) = 27x4

18.3 = solubility = 1.8 x 10!5 M

Example: What is the molar solubility of AgI in water at 25C if its Ksp is 8.3 x 10!17 at this temperature?

AgI (s) [ ]i )[ ] [ ]eq

Ag+ (aq) + 0 +x x

I! (aq) 0 +x x

Ksp = 8.3 x 10!17 = [Ag+][I!] = x2

This points out the inherent danger in comparing the solubilities of two compounds by only looking at their Ksp values. The Ksp of Ag3PO4 is smaller than that of AgI by a factor of about 30, but the molar solubility of Ag3PO4 is nearly 2000 times greater than that of AgI. Solubility and the Common-Ion Effect We are already familiar with the common-ion effect. Just as the presence of a common ion can greatly affect the dissociation of a weak acid or base, the presence of a common ion can greatly influence the solubility of a sparingly soluble salt. Consider how the presence of a common-ion affects the solubility equilibrium of AgC2H3O2 (for which Ksp = 2.0 x 10!3) in the example below. AgC2H3O2 (s) [ ]eq Ag+ (aq) + x C2H3O2! (aq) x

18.4 In a saturated solution containing only AgC2H3O2, the solubility may be expressed as either [Ag+] or [C2H3O2!]. Ksp = 2.0 x 10!3 = [Ag+][C2H3O2!] = x2

The molar solubility is therefore 4.5 x 10!2 M. Now suppose we add the soluble salt NaC2H3O2 such that the concentration of C2H3O2! from the dissolution of the NaC2H3O2 is 0.10 M. We should be able to predict, qualitatively, that the solubility of the AgC 2H3O2 will decrease in the presence of the common-ion.

AgC2H3O2 (s) [ ]i )[ ] [ ]eq

Ag+ (aq) + 0 +x x

C2H3O2! (aq) 0.10 +x 0.10 + x

Ksp = 2.0 x 10!3 = [Ag+][C2H3O2!] = (x)(0.10 + x) = 0.10 x + x2 Now we have a quadratic equation to deal with: x2 + 0.10 x ! 2.0 x 10!3 = 0 x = !0.117 or 0.0171

We can reject the negative root, so x = [Ag+] = 0.0171 M = solubility of AgC2H3O2 in the presence of 0.10 M C2H3O2 !. Here we must express the solubility of AgC 2H3O2 in terms of [Ag+] because there are now two sources of C2H3O2!, but the only source of Ag+ remains AgC 2H3O2. Precipitation Reactions We often use precipitation reactions in qualitative and quantitative analysis. qualitative analysis is a method for determining the identities of ions in a particular sample. The goal of quantitative analysis is to determine the amounts of different ions in a sample.

18.5 We have already seen how we can use the concept of a reaction quotient, Q, to determine whether or not a particular reaction is at equilibrium and if it is not, which way it must proceed in order for equilibrium to be achieved. We can apply the same reasoning to precipitation reactions. For a precipitation or solubility equilibrium, the reaction quotient is sometimes referred to as the ion-product for the reaction. Suppose we mix 100.0 mL of a 0.100 M aqueous solution of AgNO3 with 80.0 mL of a solution that is 0.0500 M in Na2SO4. Will Ag2SO4 (Ksp = 1.5 x 10!5) precipitate from this mixture? First we must consider the solubility equilibrium: Ag2SO4 (s) 2 Ag+ (aq) + SO42! (aq) Next we write the expression for the ion product of Ag2SO4 Q = [Ag+]2 [SO42!] Ksp = 1.5 x 10!5

Q = [Ag+]2 [SO42!] = (0.0555)2 (0.0222) = 6.8 x 10!5

Since Q > Ksp, Ag2SO4 will precipitate from the solution. Furthermore, the precipitation will continue as [Ag+] and [SO42!] decrease until [Ag+]2 [SO42!] = Ksp. If Q < Ksp, no precipitation will occur, and there is no equilibrium. Occasionally, Q may exceed Ksp, but precipitation does not occur immediately. In this case the solution is said to be supersaturated. A supersaturated solution is one in which the concentration of dissolved solute exceeds the solubility. This is a metastable situation, and if the solution is disturbed or a seed crystal is introduced, precipitation of the excess solute will occur immediately.

18.6 Fractional Precipitation Fractional precipitation is a technique of separating two or more ions in a solution by the addition of a reagent which will completely (or nearly completely) precipitate one ion before precipitating another. To see how this is possible, consider the following scenario. A solution contains Ag+, Pb2+ and Cu+ ions all at 0.10 M concentration. It is possible to separate these ions sequentially by the slow addition of a concentrated solution of Cl! ions. We have to consider the Ksp values for AgCl (1.8 x 10!10), PbCl2 (1.6 x 10!5) and CuCl (1.9 x 10!7). We carry out a series of calculations: 1. Calculate [Cl!] necessary to cause the precipitation of AgCl , PbCl2 and CuCl.

2. Clearly, AgCl will precipitate first, CuCl second and PbCl2 last. We now need to calculate the percentage of the Ag+ remaining when CuCl starts to precipitate and the percentage of the Cu+ remaining when the PbCl2 starts to precipitate. We will neglect the volume change on the addition of the Cl! containing solution. [Ag+] when CuCl starts to precipitate:

In other words, before any CuCl begins to precipitate, slightly more than 99.9% of the Ag+ ions have been removed.

18.7 Next we calculate the percentage of Cu+ remaining when PbCl2 first starts to precipitate.

In other words, before any PbCl2 begins to precipitate, nearly 99.99% of the Cu+ ions have been removed. Effect of pH on Solubility Thus far, we have calculated the solubility of slightly soluble salts by assuming that the solubility equilibrium was the only equilibrium that had to be taken into account. This is sometimes, but not always, the case. There are instances when one of the ions of the slightly soluble salt reacts with some other solution component and a second (or more) equilibrium must be considered. Perhaps the most common example of this is when the anion of the slightly soluble salt is also the anion of a weak acid. From our study of acid base equilibria, we know that when a salt containing the anion of a weak acid is dissolved in water, the anion can undergo hydrolysis. Consider the dissolution of BaF2 in water: BaF2 (s) Ba2+ (aq) + 2 F! (aq) You should recognize F!as the anion of a weak acid HF which will undergo hydrolysis in aqueous solutions. F! (aq) + H2O (l) HF (aq) + OH! (aq) Therefore the hydrolysis of F! will influence the solubility of BaF2 making it greater than we would calculate if we neglected this effect. This equilibrium is obviously influenced by the pH of the solution because the OH! and H3O+ concentrations are linked by the autoionization of water. 2 H2O (l) H3O+ (aq) + OH! (aq) Now the seemingly simple problem of calculating the solubility of BaF2 in aqueous solution has become somewhat more complicated because all three of these equilibria must simultaneously be satisfied. We will look at a systematic approach to studying systems where multiple simultaneous equilibria occur later. For now, however, we will just say that the solubility of a salt whose anion is the conjugate base of a weak acid increases as the pH of the solution decreases.

18.8 Lets look at an obvious example: Ksp for Pb(OH)2 at 25C is 1.2 x 10!15. What is the molar solubility of Pb(OH)2 in a) pure water and b) an aqueous solution which is buffered at pH = 7.50? a) Pb(OH)2 (s) [ ]i )[ ] [ ]eq Pb2+ (aq) + 0 +x x 2 OH! (aq) -0 +2x 2x

Ksp = 1.2 x 10!15 = [Pb2+] [OH!]2 = (x)(2x)2 = 4x3

[OH!] = 1.3 x 10!5 M [H3O+] = 10!7.50 = 3.16 x 10!8 M [OH!] = 3.16 x 10!7 M Ksp = 1.2 x 10!15 = [Pb2+] [OH!]2 = (x)(3.16 x 10!7)2

b) If pH is buffered at 7.50,

Example: What pH is necessary to prevent the precipitation of MgF2 (Ksp = 6.4 x 10!9) from a solution that is 0.10 M in MgCl2 and 0.10 M in HF (Ka = 7.1 x 10!4)? We will solve this problem in a series of steps. First, we need to calculate the [F!] at which MgF2 will precipitate in the presence of 0.10 M Mg2+. MgF2 will not precipitate if [Mg2+][F!]2 < 6.4 x 10!9.

18.9 [F!] < 2.5 x 10!4 M Next, we need to calculate the hydronium ion concentration necessary to keep the fluoride ion concentration under 2.5 x 10!4 M.

[H3O+] > 0.28 M Finally, solve for the pH. pH < 10!0.28 = 0.52

18.10 Complex-Ion Equilibria Metal ions, particularly transition metal ions, can form coordinate covalent bonds with small molecules or ions having an available lone pair of electrons.

In this reaction, Ag+ acts as a Lewis acid since it accepts a pair of electrons from each of the two NH3 molecules. Each of the NH3 molecules acts as Lewis base since each one donates an electron pair to Ag+ in the formation of two coordinate covalent bonds. Remember that in the Lewis acid-base definition, an acid is an electron pair acceptor while a base is an electron pair donor. The adduct in this case is referred to as a coordination complex or a complex ion. Complex ion: a metal ion coordinate covalently bonded to one or more molecules or ions (called ligands). If the species is neutral, it is just referred to as a coordination complex. We can write a equilibrium constant expression for the formation of the complex from the metal and the ligands according to the formation reaction. Consider the formation of the complex ion [Cu(NH3)4]2+ from Cu2+ and NH3.

Cu2+ (aq) + 4 NH3 (aq) [Cu(NH3)4]2+ (aq)

Kf is referred to as the formation (or sometimes stability) constant. The extremely large value for this particular reaction indicates that the reaction goes essentially to completion. That is, there is only a very small concentration of uncomplexed Cu2+ in solution. The dissociation constant (Kd) for a complex is simply the reciprocal of the formation constant. Kd for this reaction has a value of 2.1 x 10!13, indicating that this reaction has practically no tendency to proceed toward products.

[Cu(NH3)4]2+ (aq) Cu2+ (aq) + 4 NH3 (aq)

Coordination complexes often form in a stepwise manner. We can write four stepwise reactions for the formation of [Cu(NH3)4]2+.

18.11 Cu2+ (aq) + NH3 (aq) [Cu(NH3)]2+ (aq)

[Cu(NH3)]2+ (aq) + NH3 (aq) [Cu(NH3)2]2+ (aq)

[Cu(NH3)2]2+ (aq) + NH3 (aq) [Cu(NH3)3]2+ (aq)

[Cu(NH3)3]2+ (aq) + NH3 (aq) [Cu(NH3)4]2+ (aq)

And the overall formation constant, Kf is simply equal to the product of the stepwise formation constants: Kf = K1 x K2 x K3 x K4 = $4 Example: What is the equilibrium concentration of Cu2+ ion in a solution which is initially 0.10 M in Cu2+ and 1.0 M in NH3? Kf for [Cu(NH3)4]2+ is 4.8 x 1012. Because Kf is so large, we will assume the formation reaction goes to completion and then assume dissociation occurs to reach equilibrium. Cu2+ (aq) + 0.10 !0.10 [ ]i )[ ] [ ]eq 0 +x x 4 NH3 (aq) 1.0 !0.40 0.60 +4x 0.60 + 4x 6 [Cu(NH3)4]2+ (aq) 0 +0.10 0.10 !x 0.10 ! x

x . 1.6 x 10!13 M = [Cu2+]

Clearly x << 0.10 and 4 x << 0.60, so our assumption is justified.

18.12 Amphoteric Hydroxides An amphoteric hydroxide is a hydroxide that reacts either with an acid or a base. Most hydroxides are insoluble (except those of group IA and the heavier members of group IIA). Zn(OH)2 and Al(OH)3 are examples of insoluble amphoteric hydroxides. As expected, they react with acids to produce aqueous solutions of the cation as shown in the following equations. Zn(OH)2 (s) + 3 H3O+ (aq) 6 Zn2+ (aq) + 4 H2O (l) Al(OH)3 (s) + 3 H3O+ (aq) 6 Al3+ (aq) + 6 H2O (l) Lets consider what might happen if we gradually add concentrated aqueous NaOH to a solution containing either Zn2+ or Al3+. Since the hydroxides are relatively insoluble, we would observe the formation of solid Zn(OH)2 or Al(OH)3. What would happen if we continue to add the NaOH solution? We might predict that as [OH!] increases in the solution, Zn(OH)2 and Al(OH)3 become less and less soluble in accord with LeChateliers Principle. However, as we continue to add OH! ions, something surprising occurs. The Zn(OH)2 or Al(OH)3 precipitate suddenly dissolves as one of the following reactions occurs! Zn(OH)2 (s) + 2 OH! (aq) 6 Zn(OH)42! (aq) Al(OH)3 (s) + OH! (aq) 6 Al(OH)4! (aq)

The Effect of Complexation on Solubility Just as slightly soluble salts whose anions are the anions of weak acids become more soluble as the pH of a solution decreases, slightly soluble salts whose cations form complex ions become more soluble as ligands are added to the solution. This is readily understandable when we consider the two pertinent equilibria and Le Chateliers Principle. Consider the dissolution of AgBr in a 1.0 M NH3 solution. We consider the solubility equilibrium as well as the complexation equilibrium. AgBr (s) Ag+ (aq) + Br! (aq) Ag+ (aq) + 2 NH3 (aq) Ag(NH3)2+ (aq) Ksp = 5.0 x 10!13 Kf = 1.7 x 107

As the NH3 complexes Ag+, more AgBr must dissolve in order to maintain the concentration of Ag+ at the level required by the first equilibrium. Note that both of these equilibria must be satisfied simultaneously. In pure water the molar solubility of AgBr is 7.1 x 10!7 M.

18.13

If we assume that the NH3 concentration is not significantly altered by complexation:

and [Ag(NH3)2+] = 1.7 x 107 [Ag+] In other words, most of the dissolved silver is actually present as the ammonia complex. Now we know that all of the silver in solution comes from the dissolution of AgBr whether it be Ag+ or Ag(NH3)2+, and the dissolution of AgBr gives equal amounts of Ag+ and Br!, so [Br!] = [Ag+] + [Ag(NH3)2+] = [Ag+] + 1.7 x 107 [Ag+] . 1.7 x107 [Ag+] So,

and Ksp = 5.0 x 10!13 = [Ag+] [Br!] = 5.88 x 10!8 [Br!]2 The molar solubility of AgBr is given by [Br!]:

The concentration of NH3 is not significantly altered by complexation, and the solubility of AgBr can be taken as 0.0029 M. Your text gives a calculation of the solubility of AgCl in the presence of 1.0 M NH3. You should make it a point to work through and understand that example which shows a simplified approach to this type of problem with some implicit assumptions.

18.14 We will now take a look at a more systematic approach to problems involving multiple simultaneous equilibria. It is clear that we have ignored at least two important chemical equilibria in the previous example. Think about what they are before going any further. The two equilibria which we have until now neglected are the base ionization of NH3 and the autoionization of water. NH3 (aq) + H2O (l) NH4+ (aq) + OH! (aq) 2 H2O (l) H3O+ (aq) + OH! (aq) Kb = 1.8 x 10!5 Kw = 1.0 x 10!14

All four of these equilibria (Ksp, Kf, Kb and Kw) must be satisfied simultaneously. If we are to solve this system, we need as many independent equations as we have unknowns. What are the unknowns? The unknowns are the concentrations from the various equilibrium constant expressions.

(1)

(2)

(3)

(4)

Our unknowns are therefore [Ag+], [Ag(NH3)2+], [Br!], [NH3], [NH4+], [H3O+] and [OH!]. Since we have 7 unknowns, we must have seven independent equations in these seven unknowns. The first four of these are simply the respective equilibrium constant expressions shown directly above. Therefore, we need to find three more independent equations. The remaining equations will fall into one of two categories: 1) mass balance and 2) charge balance. The charge balance is simply a statement that the solution must be electrically neutral. That is, the total concentration of positive charges is equal to the total concentration of negative charges. For this system, the charge balance equation is: [Ag+] + [Ag(NH3)2+] + [NH4+] + [H3O+] = [OH!] + [Br!] There is only one charge balance equation for any equilibrium system. (5)

18.15 The remaining two equations are mass balance equations. These are derived from a knowledge of how the solution was prepared. If you remember, we said that the solution was initially 1.0 M in NH3. Therefore, the total concentration of NH3 in all of its forms is 1.0 M. What are the forms of NH3 in this system? We have NH3, NH4+ and Ag(NH3)2+. The concentrations of all of these species depend on the original concentration of NH3. [NH3] + [NH4+] + 2 [Ag(NH3)2+] = 1.0 M (6)

The coefficient of 2 in front of [Ag(NH3)2+] comes from the fact that there are two moles of NH3 incorporated into every one mole of Ag(NH3)2+. The second mass balance equation is one that we considered when we originally solved the problem. Since the only source of Ag+ and Br! is the dissolution of AgBr(s), the concentration of Br! must be equal to the total concentration of Ag+ in all of its forms. [Br!] = [Ag+] + [Ag(NH3)2+] (7)

Now we have a total of seven equations in seven unknowns and we can solve the system of equations for the only physically meaningful set of variables. The concentrations must be real and they must be positive.

Lets consider another situation in which multiple equilibria must be considered. Previously we alluded to the fact that solubility equilibria are strongly influenced by pH if the anion of the sparingly soluble salt is also the anion of a weak acid. Consider the solubility of AgCN in a solution whose pH is fixed at 4.00 by an appropriate buffer . For AgCN, Ksp = 2.2 x 10!16, and for HCN, Ka = 4.9 x 10!10 We can write the expression for the solubility product of AgCN as: Ksp = [Ag+][CN!] = 2.2 x 10!16 If we ignore the fact that the CN! ion will undergo hydrolysis, the solubility of AgCN is simply given by

However, to get a better value of the solubility, we must take into account the fact that some of the cyanide will undergo hydrolysis, since HCN is a weak acid. HCN (aq) + H2O (l) H3O+ (aq) + CN! (aq) or CN! (aq) + H2O (l) HCN (aq) + OH! (aq) Kb = 2.0 x 10!5 Ka = 4.9 x 10!10

18.16 These do not give rise to independent equations since one is derived from the other. A third equation is the autoionization of water: 2H2O (l) H3O+ (aq) + OH! (aq) Kw = 1.0 x 10!14

In general we would have five unknowns and would therefore require two additional equations, the mass balance and charge balance equations to solve this system. [Ag+] = [CN!] + [HCN] [Ag+] + [H3O+] = [CN!] + [OH!] (mass balance) (charge balance)

However, the buffer fixes both [H3O+] and [OH!] as well as the ratio of [CN!] to [HCN], greatly simplifying the problem.

But at pH = 4.00, [H3O+] = 1.0 x 10!4 M

Rearranging

and inverting

so, [HCN] = 2.0 x 105 [CN!] Substituting back into our mass balance equation: [Ag+] = [CN!] + 2.0 x 105 [CN!] . 2.0 x 105 [CN!]

18.17 We express the solubility of AgCN in terms of [Ag+]

So

This is a solubility 440 times greater than we calculated without taking the hydrolysis of CN! into account. Alpha Values Previously we looked at a distribution curve for a generic weak acid HA. This curve gave the relative concentrations of HA and A! at various values of pH. In general, we can generate such curves for any acid if we know the value(s) of its ionization constant(s). Consider a 0.10 M aqueous solution of phosphoric acid, H3PO4, a weak triprotic acid.

H3PO4(aq) + H2O(l) 6 H3O+(aq) + H2PO4!(aq)

H2PO4!(aq) + H2O(l) H3O+(aq) + HPO42!(aq)

HPO42!(aq) + H2O(l) H3O+(aq) + PO43!(aq)

Depending on the pH, there are four different phosphate containing species that can exist, H3PO4, H2PO4!, HPO42! and PO43!. The total phosphate concentration is given by the sum of these concentrations. This is our mass balance equation. 0.10 M = CT = [H3PO4] + [H2PO4!] + [HPO42!] + [PO43!] The fractional concentrations of these species are given by the concentration of the particular species over the sum of the concentrations of all the phosphate containing species, and are designated as " values:

18.18

The sum of all the " values for any system must be unity. Therefore, in the H3PO4 system: "0 + "1 + "2 + "3 = 1

18.19 Now, we substitute these values in the mass balance expression.

Factoring out [H3PO4],

Now multiply each side by [H3O+]3.

Now we rearrange:

By similar manipulations, we can show that :

18.20 Notice that the denominator is the same in each " expression, and the numerator of the successive " values consists of each successive term in the denominator. This is a general result which can be applied to any acid, whether it be polyprotic or monoprotic. The first term in the denominator is always [H3O+] raised to a power corresponding to the number of protons an acid can provide. In each successive term, the power to which the [H3O+] is raised is reduced by one and a successive value of K is introduced. For a diprotic acid, D = [H3O+]2 + K1 [H3O+] + K1 K2 For a monoprotic acid, D = [H3O+] + K1

18.21 Now lets reconsider the solubility of AgCN in a solution buffered at pH = 4.00. We know that our mass balance must hold: [Ag+] = [CN!] + [HCN] and our solubility equilibrium must hold: At pH = 4.00, 2.2 x 10!16 = [Ag+] [CN!]

2.2 x 10!16 = [Ag+] [CN!] = 4.9 x 10!6 [Ag+]2