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Chapter 18
The Solubility Product Constant
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Write the net ionic equation
• Solutions of sodium chromate and barium chloride are mixed.
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Ba2+ + CrO42- → BaCrO4
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Ba2+ + CrO42- ↔ BaCrO4
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BaCrO4 ↔ Ba2+ + CrO42-
• Since the reaction is reversible when can flip it.• Write the equilibrium expression for this reaction.
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BaCrO4 ↔ Ba2+ + CrO42-
K = [Ba2+] [CrO42-]
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BaCrO4 ↔ Ba2+ + CrO42-
Ksp = [Ba2+] [CrO42-]
• This is the solubility product expression
• It is used to determine the concentrations of ions in a saturated solution of a slightly soluble salt and determine whether a precipitate will form within a solution.
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Write the solubility product expression for AgCl
Ksp = [Ag+] [Cl-]
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Write the solubility product expression for MgF2
Ksp = [Mg2+] [F-]2
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Write the solubility product expression for Ag3PO4
Ksp = [Ag+]3 [PO43-]
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Molar Solubility
• Molar solubility is the maximum solubility of a substance expressed in moles per liter.
• Example: The molar solubility of silver chromate (Ag2CrO4) is 1.3 x 10-4 mol/L
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The molar solubility of Hg2Cl2 is 6.5 x 10-7 mol/L.
Find the solubility product.
Ksp = 1.1 x 10-18
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The molar solubility of Ag2CrO4 is 1.3 x 10-4 mol/L.
Find the solubility product.
Ksp = 8.8 x 10-12
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The solubility of PbCrO4 is 4.30 x 10-5 g/L. Find the solubility product.
What’s the difference here?
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The solubility of PbCrO4 is 4.30 x 10-5 g/L. Find the solubility product.
Ksp = 1.8 x 10-14
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The solubility of PbCrO4 is 4.30 x 10-5 g/L. Find the solubility product.
Ksp = 1.8 x 10-14
See Appendix D (Pages A6 & A7)
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What is the molar solubility PbCrO4?Ksp of PbCrO4 = 1.8 x 10-14
Molar solubility = 1.3 x 10-7 mol PbCrO4/L
[Pb2+] = [CrO42-] = 1.3 x 10-7 M
What are the ion concentrations?
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What is the molar solubility Ag2CrO4?Ksp of Ag2CrO4 = 8.8 x 10-12
Molar solubility = 1.3 x 10-4 mol Ag2CrO4/L
[Ag+] = 2.6 x 10-4 M [CrO42-] = 1.3 x 10-4 M
What are the ion concentrations?
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What is the molar solubility Ag3PO4?Ksp of Ag3PO4 = 1.8 x 10-18
Molar solubility = 1.6 x 10-5 mol Ag3PO4/L
[Ag+] = 4.8 x 10-5 M [PO43-] = 1.6 x 10-5 M
What are the ion concentrations?
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What is the molar solubility Pb3(PO4)2?
Ksp of Pb3(PO4)2 = 3.0 x 10-44
Molar solubility = 7.7 x 10-10 mol Pb3(PO4)/L
[Pb2+] = 2.3 x 10-9M [PO43-] = 1.5 x 10-9 M
What are the ion concentrations?
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I place a large scoopful of Ag3PO4 (a white crystalline solid) in a beaker of water and stir. I come back tomorrow.
What do I see in the beaker?
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Did any of the Ag3PO4 dissolve?
What are the concentrations in the solution?
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What is the molar solubility Ag3PO4?Ksp of Ag3PO4 = 1.8 x 10-18
Molar solubility = 1.6 x 10-5 mol Ag3PO4/L
[Ag+] = 4.8 x 10-5 mol Ag+/L [PO4
3-] = 1.6 x 10-5 mol PO43-/L
What are the ion concentrations?
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Did any of the Ag3PO4 dissolve? If any does dissolve what are the concentrations in the solution?
[Ag+] = 4.8 x 10-5M [PO4
3-] = 1.6 x 10-5M
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How would you describe this solution?
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Saturated Solutions and Solubility
Crystallization: opposite of the solution process (solute becomes reattached to surface of crystal)
Saturated solution: no more solid will dissolve and a dynamic equilibrium exists between the solution and the undissolved solid.
Solute + Solvent Solution
ecrystalliz
dissolve
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What would we observe if we added sodium phosphate solution to a beaker saturated
solution of Ag3PO4?
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What would we observe if we added sodium phosphate solution to the beaker containing a
saturated solution of Ag3PO4?
Ksp of Ag3PO4 = 1.8 x 10-18
[Ag+] = 4.8 x 10-5 mol Ag+/L[PO4
3-] = 1.6 x 10-5 mol PO43-/L
[Ag+]3[PO43-]
= [4.8 x 10-5]3 [1.6 x 10-5] = ?
Why does Ag3PO4 precipitate?
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Reaction Quotient
If Q = Ksp, the system is at equilibrium and the solution is saturated
If Q < Ksp, the solution is not saturated precipitate does not form
If Q > Ksp, the solution exceeds saturation and a precipitate forms
Q vs Ksp
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Does AgCl precipitate when equal volumes of 1.5 x 10-5M solutions of AgNO3 and NaCl mix?
??
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Does AgCl precipitate when equal volumes of 1.5 x 10-5M solutions of AgNO3 and NaCl mix?
NO
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Does AgCl precipitate when equal volumes of 1.5 x 10-5M solutions of AgNO3 and NaCl mix?
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200.0ml of 0.0015M MgCl2 is mixed with 100.0ml of 0.0015M NaOH. Does Mg(OH)2 precipitate?
??
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200.0ml of 0.0015M MgCl2 is mixed with 100.0ml of 0.0015M NaOH. Does Mg(OH)2 precipitate?
Yes
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200.0ml of 0.0015M MgCl2 is mixed with 100.0ml of 0.0015M NaOH. Does Mg(OH)2 precipitate?
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AgNO3 solution is added to a solution of Na2CrO4. What precipitate forms?
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AgNO3 is added to a 0.0010M solution of Na2CrO4. What is the [Ag+] when the Ag2CrO4 precipitate begins to form?
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Clothing washed in water that has a manganese concentration exceeding 0.1 mg L-1 (1.8 x 10-6 M) may be stained with manganese. A laundry wishes to add a base to precipitate manganese as the hydroxide Mn(OH)2 (Ksp = 4.5 x 10-14). At what pH is [Mn2+] equal to 1.8 x 10-6 M?
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Clothing washed in water that has a manganese concentration exceeding 0.1 mg L-1 (1.8 x 10-6 M) may be
stained with manganese. A laundry wishes to add a base to precipitate manganese as the hydroxide Mn(OH)2 (Ksp = 4.5
x 10-14). At what pH is [Mn2+] equal to 1.8 x 10-6 M?
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Fractional Precipitation
• The process by which two aqueous substances in a solution are separated through the addition of a common ion, taking advantage of their different concentration needs (Ksp values) in order to form a precipitate.
• The ion with the ________ Ksp will precipitate first.
smaller
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A solution contains 0.010 mol of KI and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution.
Which precipitate forms first, AgCl or AgI?
• This is a multiple equilibria problem.
• Strategy: If there is more than one equilibrium involved write both and solve for what you can.
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A solution contains 0.010 mol of KI and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution.
Which precipitate forms first, AgCl or AgI?
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A solution contains 0.010 mol of KI and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution. What is the [I ̄ ] in the solution when AgCl starts to precipitate?
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A solution contains 0.010 mol of KI and 0.10 mol of KCl per liter. AgNO3 is gradually added to this solution. What percent of the
original [I ̄ ] remains in solution when AgCl starts to precipitate?
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NH4Cl is added to a 750mL solution that is 0.10M in Mg2+ and 0.10M in NH3. The solution also contains a Mg(OH)2 precipitate.
Calculate the [NH4+] that is required to dissolve the precipitate.
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NH4Cl is added to a 750mL solution that is 0.10M in Mg2+ and 0.10M in NH3. The solution also contains a Mg(OH)2 precipitate.
How many grams of NH4Cl were added?
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We can increase or decrease the solubility of “insoluble” (slightly soluble) substances by
applying LeChatlier’s Principle.
• The Common Ion Effect
• pH
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The Common-Ion Effect
• A salt is less soluble in a solution that has an ion in common with the salt.
• Calcium Sulfate (CaSO4) is “insoluble” (slightly soluble) in water.
• Write the equation that represents the solubility of calcium sulfate in water.
CaSO4(s) ⇌ Ca2+(aq) + SO42−(aq)
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The Common-Ion Effect
CaSO4(s)⇌Ca2+(aq)+SO42−(aq)
• Describe the equilibrium system of Calcium Sulfate in water.
•The solution is saturated with most of the calcium sulfate in solid form.
•The [SO42−] in the solution is very
low and is equal to the [Ca2+].
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The Common-Ion Effect
CaSO4(s)⇌Ca2+(aq)+SO42−(aq)
• Describe what would happen if a solution of sodium sulfate were added to the beaker.
•The [SO42−] would increase
causing the reaction to shift to the left reducing the solubility of CaSO4 causing the it CaSO4 to precipitate out of the solution.
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pH
• The pH can affect the solubility of a solute in two ways: – through the common ion effect.
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Al(OH)3 ↔ Al3+ + 3OH ?
• Is Al(OH)3 more soluble at a lower pH, higher pH, or does pH not affect the solubility of Al(OH)3 ?
Confused?
• What happens to this equilibrium if a strong base such as NaOH is added?
• What happens to this equilibrium if a strong acid such as HCl is added?
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pH
• The pH can affect the solubility of a solute in two ways: – through the common ion effect.
or– when a salt contains a basic anion such as F–,
CH3CO2–, or CN– it is normally more soluble at
low pH’s.– When a salt contains an acidic ion such as Ag+,
Zn2+, or Al3+ it is often normally more soluble at high pH’s.
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FeS ↔ Fe2+ + S2-
• What happens to this equilibrium if a strong acid such as HCl is added?
• A strong acid such as HCl will often dissolve an insoluble salt by lowering the concentration of the anion from the solution and forming a weak acid.
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AgCl ↔ Ag+ + Cl ?
• What happens to this equilibrium if ammonia or a strong base is added?
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Adding Strong Bases or Ammonia to Insoluble Salts
• A strong base or ammonia will often dissolve an insoluble salt by lowering the concentration of the cation from the solution and forming a complex ion.
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