The Solubility Product

Chapter 20

Solubility Product Constants

Silver chloride, AgCl,is rather insoluble in water. Careful experiments show that if solid AgCl is placed in pure water and vigorously stirred, a small amount of the AgCl dissolves in the water. Ag+Cl-(s) Ag+(aq) + Cl-(aq)

Solubility Product Constants

The equilibrium constant expression for this dissolution is called a solubility product constant. Ksp = solubility product constant Ksp = [Ag+][Cl-] = 1.8 x 10-10

Solubility Product Constants

The solubility product constant, Ksp, for a compound is the product of the concentrations of the constituent ions, each raised to the power that corresponds to the number of ions in one formula unit of the compound. Examples: Ag2S(s) 2Ag+(aq) + S2-(aq) Ksp = [Ag+]2[S2-] =1.0 x 10-49 Ca3(PO4)2(s) 3Ca+2(aq) + 2PO43-(aq) Ksp = [Ca+2]3[PO4-3]2 = 1.0 x 10-25 CaNH4PO4(s) Ca+2(aq) NH4+ + PO43-(aq) Ksp = [Ca2+][NH4+][PO43-]
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Ksp Table
All Ksp values are small. All salts are only slightly soluble

Determination of Solubility Product Constants

One liter of saturated silver chloride solution contains 0.00192 g of dissolved AgCl at 25C. Calculate the molar solubility of, and Ksp for, AgCl.

Dissociation: AgCl(s) Ag+(aq) + Cl-(aq)

Molar solubility:
0.00192 gAgCl L x 1 molAgCl 143 gAgCl = 1.34 x 10-5 molAgCl L

Ksp: Ksp = [Ag+][Cl- ]

Ksp =1.80 x 10-10

Ksp = [1.34 x 10-5 ][1.34 x 10-5 ]

Determination of Solubility Product Constants

One liter of saturated calcium fluoride solution contains 0.0167 gram of CaF2. Calculate the molar solubility of, and Ksp for, CaF2. Dissociation: CaF2(s) Ca2+(aq) + 2F-(aq) Molar solubility:
0.0167 gCaF2 L x 1 molCaF2 78.1 gCaF2 = 2.14 x 10-4 molCaF2 L

Ksp: K = [Ca2+][F- ]2 sp
Ksp =3.92 x 10-11 or

Ksp = [2.14 x 10-4 ][2 x 2.14 x 10-4 ]2

Ksp = [x][2x]2 = 4x3 = 4(2.14 x 10-4 )3 Ksp =3.92 x 10-11

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EOC #6, page 790

Example 20-1 Write the solubility product expression for each of the following salts: (a) Mn3(AsO4)2 (b) Hg2I2 [contains mercury (I) ions, Hg22+] (c) AuI3 (d) SrCO3 (a) Mn3(AsO4)2; Ksp = [Mn2+]3[AsO43-]2 (3x)3(2x)2 = 108x5 (b) Hg2I2; Ksp = [Hg22+][I-]2 (x)(2x)2 = 4x3 (c) AuI3; Ksp = [Au3+][I-]3 (x)(3x)3 = 27x4 (d) SrCO3; Ksp = [Sr2+][CO32-] (x)(x) = x2

EOC #8, page 767

Example 20-2
Given the solubility data for the following compounds, calculate their solubility product constants. (a) SrCrO4, strontium chromate, 1.2 mg/mL (b) BiI3, bismuth iodide, 7.7 x 10-3 g/L (c) Fe(OH)2, iron(II) hydroxide, 1.1 x 10-3 g/L (d) SnI2, tin(II) iodide, 10.9 g/L (a) SrCrO4, 1.2 x 10-3g 204 g/mol 1.0 x 10-3L = 5.9 x 10-3 M

Ksp = x2 = (5.9 x 10-3)2 = 3.5 x 10-5 (b) BiI3, (27x4) and Ksp = 7.7 x 10-19 (c) Fe(OH)2, (4x3) and Ksp = 6.9 x 10-15 (d) SnI2, (4x3) and Ksp = 1.01 x 10-4

Uses of Ksp
Calculate the molar solubility of barium sulfate, BaSO4, in pure water and the concentration of barium and sulfate ions in saturated barium sulfate.

Dissociation: BaSO4(s) Ba2+(aq) + SO42-(aq) Molar solubility: Ksp = (x)(x) = x2 = 1.1 x 10-10

x = 1.1 x 10-10 x = 1.0 x 10-5 M

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Uses of Ksp
Calculate the mass of barium sulfate, BaSO4, in 1.00 L of saturated solution Dissociation: BaSO4(s) Ba2+(aq) + SO42-(aq) Molar solubility: x = 1.0 x 10-5 Mass:
234 gBaSO4 molBaSO4 x 1.0 x 10-5 molBaSO4 L x L = 2.3 x 10-3 gBaSO4
(from previous slide)

g FW x M x L = g from M = FW L

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Uses of Ksp
The Ksp for magnesium hydroxide, Mg(OH)2, is 1.5 x 10-11. Calculate the molar solubility of magnesium hydroxide and the pH of saturated magnesium hydroxide solution. Dissociation: Mg(OH)2(s) Mg2+(aq) + 2OH-(aq) Molar solubility: Ksp = [Mg2+][OH-]2 = (x)(2x)2 = 4x3 = 1.5 x 10-11 ; x = 1.6 x 10-4 [molar solubility] [OH-] = 2 x molar solubility = 3.2 x 10-4 pOH = 3.49 and pH = 10.51

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Uses of Ksp
Calculate the concentration of calcium ion in a calcium phosphate, Ca3(PO4)2, in pure water. Ksp= 2.1 x 10-33. Dissociation: Ca3(PO4)2 3Ca2+ + 2PO43Molar solubility: Ksp = [Ca2+]3[PO43-]2 = (3x)3 (2x)2 = (27x3)(4x2) = 108x5 = 2.1 x 10-33 x = 1.1 x 10-7 [molar solubility] [Ca2+] = 3 x molar solubility = 3.3 x 10-7

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EOC #16, page 790

Example 20-3
Calculate molar solubilities, concentrations of ions, and solubilities in grams per liter for the following compounds at 25 C: (a) CuCl, copper(I) chloride (b) Ba3(PO4)2, barium phosphate (c) PbI2, lead fluoride (d) Sr3(PO4)2, strontium phosphate (a) CuCl: x2 = Ksp = 1.9 x 10-7; x = 4.4 x 10-4 M (MS) (4.4 x 10-4 mol/L) x (99 g/mol) = 0.043 g/L (b) Ba3(PO4)2: MS = 6.5 x 10-7 (3.9 x 10-4 g/L) (c) PbI2: MS = 2.1 x 10-3 (0.51 g/L) (d) Sr3(PO4)2: MS = 2.5 x 10-7 (1.1 x 10-4 g/L)
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Common Ion Effect

Solubility is decreased when a common ion is added. This is an application of Le Chteliers principle: BaSO4 Ba2+ + SO42As SO42- (from Na2SO4, say) is added, the equilibrium shifts away from the increase. Therefore, BaSO4(s) is formed and precipitation occurs. As Na2SO4 is added to the system, the solubility of BaSO4 decreases.

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Common Ion Effect

Calculate the molar solubility of barium sulfate, BaSO4, in 0.010 M sodium sulfate, Na2SO4, solution. Compare this to the solubility of BaSO4 in pure water. Write equations to represent the equilibria:

Na2SO4 2 Na+ + SO420.010 x

2(0.010) Ba+2 x

0.010 + SO42x BaSO4

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Common Ion Effect

Substitute the concentrations into the Ksp expression and solve for x. Ksp = [Ba2+][SO42-] = 1.1 x 10-10 Ksp = (x)(0.010) = 1.1 x 10-10 MS = x = 1.1 x 10-8 The molar solubility of BaSO4 in 0.010 M Na2SO4 solution is 1.1 x 10-8 M. The molar solubility of BaSO4 in pure water is 1.0 x 10-5 M. 900 times greater
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EOC #20, page 790

Example 20-4 Calculate the molar solubility of Ag2SO4 in 0.12 M K2SO4 solution. K2SO4 2K+ + SO42Ag2SO4 2Ag+ + SO422x + (x + 0.12) Ksp = 1.7 x 10-5 = (2x)2 0.12; x = 6.0 x 10-3 MS = 6.0 x 10-3 mol Ag2SO4/L in 0.12 M K2SO4

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EOC #26, page 791

Example 20-4 Which has the greater molar solubility in a 0.125 M K2CrO4 solution: BaCrO4 or Ag2CrO4? BaCrO4: Ksp = x(0.125) = 2.0 x 10-10; x = 1.6 x 10-9 Ag2CrO4: Ksp = (2x)2(0.125) = 9.0 x 10-12; x = 4.2 x 10-6 Ag2CrO4 is more soluble

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The Reaction Quotient

We mix 100 mL of 0.010 M potassium sulfate, K2SO4, and 100 mL of 0.10 M lead (II) nitrate, Pb (NO3)2 solutions. Will a precipitate form [PbSO4]? K2SO4 2K+ + SO42Pb(NO3)2 Pb2+ + 2NO3Solution volumes are additive. Concentrations of the important ions are: 100 mL x 0.10 M 200 mL = 0.050 M Pb2+ 100 mL x 0.010 M 200 mL = 0.0050 M SO42Qsp = [Pb2+][SO42-] = (0.050)(0.0050) = 2.5 x 10-4 Ksp = 1.8 x 10-8 for PbSO4 Qsp > Ksp therefore precipitate forms
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The Reaction Quotient

Suppose we wish to remove mercury from an aqueous solution that contains a soluble mercury compound such as Hg(NO3)2. We can do this by precipitating mercury(II) ions as the insoluble compound HgS. What concentration of sulfide ions, from a soluble compound such as Na2S, is required to reduce the Hg2+ concentration to 1.0 x 10-8 M? For HgS, Ksp=3.0 x 10-53. Ksp = [Hg2+][S2-] Ksp = [1.0 x 10-8][S2-] = 3.0 x 10-53 [S2-] = [3.0 x 10-53] [1.0 x 10-8]= 3.0 x 10-45 M Add enough S2-, in the form of Na2S, to just slightly exceed 3.0 x 10-45 M
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Separating Salts
A solution contains 0.020 M Ag+ and Pb2+. Add CrO42- to precipitate red Ag2CrO4 and yellow PbCrO4. Which precipitates first? Ksp for Ag2CrO4 = 9.0 x 10-12 Ksp for PbCrO4 = 1.8 x 10-14 Solution The substance whose Ksp is first exceeded precipitates first. The ion requiring the lesser amount of CrO42precipitates first.
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Separating Salts
A solution contains 0.020 M Ag+ and Pb2+. Add CrO42- to precipitate red Ag2CrO4 and yellow PbCrO4. Which precipitates first? Ksp for Ag2CrO4 = 9.0 x 10-12 and Ksp for PbCrO4 = 1.8 x 10-14 Solution:Calculate [CrO42-] required by each ion. [CrO42-]to ppt. PbCrO4 = Ksp/[Pb2+] = 1.8 x 10-14 / 0.020 = 9.0 x 10-13 M [CrO42-]to ppt. Ag2CrO4 = Ksp / [Ag+]2 = 9.0 x 10-12 / (0.020)2 = 2.3 x 10-8 M Qsp Ag2CrO4>Qsp PbCrO4 so PbCrO4 precipitates first.
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Separating Salts
How much Pb2+ remains in solution when Ag+ begins to precipitate? Solution We know that [CrO42-] = 2.3 x 10-8 M to begin to ppt. Ag2CrO4. What is the Pb2+ conc. at this point? Solution [Pb2+] = Ksp / [CrO42-] = 1.8 x 10-14 /2.3 x 10-8 = 7.8 x 10-7 M Lead ion has dropped from 0.020 M to < 10-6M

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Separating Salts
%unppt = %unppt = [unppt] x 100% [original] 7.8 x 10-7 x 100% = 0.0039% 0.020

99.9961% of Pb2+ ions precipitates before AgCrO4 begins to precipitate.

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EOC #28, page 791

Example 20-5 Will a precipitate of PbCl2 form when 5.0 g of solid Pb(NO3)2 is added to 1.00 L of 0.010 M NaCl? Assume assume that the volume change is negligible. PbCl2 Pb2+ +2Cl-; Ksp = 1.7 x 10-5 [Pb2+] = 5.0 g 331 g/mol = 0.015 M [Cl-] = [NaCl] = 0.010 M Qsp = (0.015)(0.010)2 = 1.5 x 10-6 Qsp < Ksp therefore there will be no precipitate
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EOC #29, page 791

Example 20-6 Sodium bromide and lead nitrate are soluble in water. Will lead bromide precipitate when 1.03 g of NaBr and 0.332 g of Pb(NO3)2 are dissolved in sufficient water to make 1.00 L of solution? PbBr2 Pb2+ +2Br-; Ksp = 6.3 x 10-6 [Pb2+] = 0.332 g 331 g/mol = 0.00100 M [Br-] = [NaBr] = 1.03 g 103 g/mol = 0.0100 M Qsp = (0.00100)(0.0100)2 = 1.00 x 10-7 Qsp < Ksp therefore there will be no precipitate
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EOC #32, page 791

Example 20-7 A solution is 0.0100 M in Pb2+ ions. If 0.103 mol of solid NaI is added to 1.00L of this solution (with negligible volume change), what percent of the Pb2+ ions remain in solution? 0.010 0.103 Pb+2 + 2NaI PbI2; PbI2 Pb+2 + 2IKsp = (x)(2x + (0.103 - 0.020))2 = 8.7 x10-9 [Pb+2] or x = 1.3 x 10-6 x<<0.083 or 0.103 - 0.020 %unppt = (1.3 x 10-6) (0.0100) x 100% %unppt = 0.013%
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Fractional Precipitation
Fractional precipitation is a method of precipitating some ions from solution while leaving others in solution. Look at a solution that contains 0.010 M each of Cu+, Ag+, and Au+ We can precipitate them as chlorides CuCl Cu+ + Cl- Ksp = [Cu+][Cl-] = 1.9 x 10-7 AgCl Ag+ + Cl- Ksp = [Ag+][Cl-] = 1.8 x 10-10 AuCl Au+ + Cl- Ksp = [Au+][Cl-] = 2.0 x 10-13 Gold will precipitate first and copper will be last as we slowly add NaCl
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Fractional Precipitation
Concentration of Cl- required to precipitate each metal ion.

For Au+ - Ksp =[Au+][Cl- ] = 2.0 x 10-13 [Cl- ]= 2.0 x 10-13 2.0 x 10-13 = = 2.0 x 10-11 M [Au+] 0.010 1.8 x 10-10 1.8 x 10-10 = = 1.8 x 10-8 M [Ag+] 0.010 1.9 x 10-7 1.9 x 10-7 = = 1.9 x 10-5 M [Cu+] 0.010
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For Ag+ - Ksp =[Ag+][Cl- ] = 1.8 x 10-10 [Cl- ]=

For Cu+ - Ksp =[Cu+][Cl- ] = 1.9 x 10-7 [Cl- ]=

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Fractional Precipitation
We have calculated the [Cl-] required to precipitate AuCl, [Cl-] > 2.0 x 10-11 M to precipitate AgCl, [Cl-] > 1.8 x 10-8 M to precipitate CuCl, [Cl-] > 1.9 x 10-5 M We can calculate the amount of Au+ precipitated before Ag+ begins to precipitate, as well as the amounts of Au+ and Ag+ precipitated before Cu+ begins to precipitate.

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Fractional Precipitation
Calculate the percent of Au+ ions that precipitate before AgCl begins to precipitate. Use the [Cl-] = 1.8 x 10-8 M to determine the [Au+] remaining in solution just before AgCl begins to precipitate.
For Au+ - Ksp =[Au+][Cl- ] = 2.0 x 10-13 [Au+]= 2.0 x 10-13 2.0 x 10-13 = = 1.1 x 10-5 M unppt [Cl- ] 1.8 x 10-8 [unppt] %unppt = x 100% [original] %unppt = 1.1 x 10-5 x 100% = 0.11% 0.010 Therefore 99.89 % of the Au+ has precipitated
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before AgCl begins to precipitate.

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Fractional Precipitation
Calculate the percent of Ag+ ions that precipitate before CuCl begins to precipitate. Use the [Cl-] = 1.9 x 10-5 M to determine the [Ag+] remaining in solution just before CuCl begins to precipitate.
For Ag+ - Ksp =[Ag+][Cl- ] = 1.8 x 10-10 [Ag+]= 1.8 x 10-10 1.8 x 10-10 = = 9.5 x 10-6 M unppt [Cl- ] 1.9 x 10-5 [unppt] %unppt = x 100% [original] %unppt = 9.5 x 10-6 x 100% = 0.095% 0.010 Therefore 99.905 % of the Ag+ has precipitated
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before AgCl begins to precipitate.

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EOC #36, page 791

Example 20-8 & 20-9
To a solution that is 0.010 M in Cu+, 0.010 M in Ag+, and 0.010 M in Au, solid NaBr is added slowly. Assume that there is no volume change due to the addition of solid NaBr. (a) which compound will begin to precipitate first? (b) Calculate [Au+] when AgBr just begins to precipitate. What percentage of the Au+ has precipitated at this point? (c) Calculate [Au+] and [Ag+] when CuBr just begins to precipitate.

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EOC #38, page 791

Example 20-8 & 20-9
A solutionhave similar ion SO4 andPbCrO4in K2CrO4. A (a) Both is 0.050 M in K2 ratio - 0.050 has the solution Ksp and will is added slowly without changing smaller of Pb(NO3)2 ppt first. the volume appreciably. (a) Which salt, PbSO4 or PbCrO4, will precipitate first? (b) What is [Pb2+] when (b) PbCrO4 will ppt when Qsp = [Pb2+][CrO42-] = Ksp the salt in part (a) begins to precipitate? (c) What is = 1.8 x 10-14 so [Pb2+] = Ksp [CrO42-] = 1.8 x [Pb2+] when the other salt -13 begins to precipitate? -14

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0.050 = 3.6 x 10

(c) PbSO4 will ppt when Qsp = [Pb2+][SO42-] = Ksp = 1.8 x 10-8 so [Pb2+] = Ksp [SO42-] = 1.8 x 10-8 0.050 = 3.6 x 10-7

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EOC #46, page 791

Example 20-10 If a solution is 2.0 x 10-5 M in Mn(NO3)2 and 1.0 x 10-3 M in aqueous ammonia, will Mn(OH)2 precipitate? Mn(OH)2 Mn2+ + 2OHNH3 + H2O NH4+ + OHKsp = 4.6 x 10-14 Kb = 1.8 x 10-5

[Mn2+] = [Mn(NO3)2] = 2.0 x 10-5 [OH-] = ionization of NH3 Qsp = [Mn2+][OH-] = 3.4 x 10-13 Qsp>Ksp - a ppt will form
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Kb = [NH3][OH-] [NH3] = x2 (1.0 x 10-3); x = 1.3 x 10-4

SKIP and stop for test

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Simultaneous Equilibria
If 0.10 mole of ammonia and 0.010 mole of magnesium nitrate, Mg(NO3)2, are added to enough water to make one liter of solution, will magnesium hydroxide precipitate from the solution? For Mg(OH)2, Ksp = 1.5 x 10-11; Kb for NH3 = 1.8 x 10-5. Calculate Qsp for Mg(OH)2 and compare it to its Ksp. Mg(NO3)2 is a soluble ionic compound so [Mg2+] = 0.010 M. Aqueous ammonia is a weak base that we can calculate [OH-] Same type of problem as the last EOC [OH-] = 1.3 x 10-3 and [Mn2+] = 0.010 Qsp = 1.7 x 10-8 Qsp>Ksp
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Simultaneous Equilibria
How many moles of solid ammonium chloride, NH4Cl, must be used to prevent precipitation of Mg (OH)2 in one liter of solution that is 0.10 M in aqueous ammonia and 0.010 M in magnesium nitrate, Mg(NO3)2? Calculate the maximum [OH-] that can exist in a solution that is 0.010 M in Mg2+. Kb = [Mg2+][OH-] = 1.5 x 10-11 [OH-] = Kb [Mg2+] [OH-] = 1.5 x 10-11 0.010 = 3.9 x 10-5 M

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Simultaneous Equilibria
Using the maximum [OH-] that can exist in solution, we can calculate the number of moles of NH4Cl required to buffer 0.10 M aqueous ammonia so that [OH-] does not exceed 3.9 x 10-5 M.
(0.10 - 3.9 x 10-5)

NH3
xM

+ H2O

3.9 x 10-5 NH4+ xM

+ +

3.9 x 10-5 -

OH
xM

NH4Cl
(0.10 - 3.9 x 10-5)

NH4+

Cl3.9 x 10-5 -

NH3

+ H2O

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xM + 3.9 x 10-5 NH4+ + x >> 3.9 x 10-5

OH

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Simultaneous Equilibria
Kb = Kb = [NH+][OH- ] 4 =1.8 x 10-5 [NH3 ] (x +(3.9 x 10-5 ))(3.9 x 10-5 ) =1.8 x 10-5 (0.10 - (3.9 x 10-5 ))

(3.9 x 10-5 )2 << x so (x +(3.9x10-5 ))(3.9 x 10-5 ) = x(3.9 x 10-5 )

Kb =

x(3.9 x 10-5 ) =1.8 x 10-5 (0.10) x = 0.046 M =[NH4Cl]= 0.046mol / L

CHECK :Qsp = Ksp at equilibrium

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EOC #42, page 791

Example 20-11 & 20-12 If a solution is made 0.080 M in Mg(NO3)2, 0.075 M in aqueous ammonia, and 3.5 M in NH4NO3, will Mg (OH)2 precipitate? What is the pH of this solution?
Mg(OH)2 Mg2+ + 2OHNH3 + H2O NH4+ + OHKsp = 1.5 x 10-11 Kb = 1.8 x 10-5

[Mg2+] = [Mg(NO3)2] = 0.080 M [OH-] = Kb x [base]/[salt] (see chapter 18 - buffers) [OH-] = (1.8 x 10-5)(0.075 M)(3.5 M) = 3.9 x 10-7
Qsp = [Mg2+][OH-]2 = (0.080)(3.9 x 10-7)2 = 1.2 x 10-14

Qsp<Kb ; Mg(OH)2 will not precipitate

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[OH-] = 3.9 x 10-7 ; pOH = 6.41; pH = 7.59

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