Chapter 17: Solubility Equilibria

Solubility Equilibria (Ksp) (Sections 17.1-17.2)

WHY?
Many ionic compounds are very soluble in water while other are very insoluble. This situation results from the
balance that is truck between the lattice energy of the ions in the solid, the hydration energy when the ions go into
solution, and the change in entropy when a solution is formed. An equilibrium constant, which is called the
solubility product constant (Ksp), is used to indicate the extent to which any ionic solid is soluble. The Ksp allows
one to predict how much of any compound will dissolve, how conditions like pH and common ions affect the
solubility, and which ionic compound of several possibilities will precipitate first as conditions change.

Key Questions:
1. According to the solubility rules above, what does it mean for a salt to be “insoluble”?

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Chapter 17: Solubility Equilibria

Key Questions:
2. Describe the general form of the reactions in the model? What do the reactions describe?

3. How is the form of the solubility product constant (Ksp) similar to, and how does it differ
from equilibrium constants we have studied thus far (Kc, Kp, Ka, Kb, Kw)?

4. Is silver chloride or sodium chloride more solubility in water? Explain how specific
information in the Model supports your conclusion?

5. What units would be appropriate to describe the solubility of a salt?

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Chapter 17: Solubility Equilibria

6. Carefully consider the situation for lead(II) iodide and lead (II) sulfate in the model. In
determining which salt is more soluble, what information needs to be taken into account in
addition to the Ksp values?

7. Suppose chloride ions could be remove selectively from the AgCl solution in the Model.
According to Le Chatlier’s principle, how would this affect the silver ion concentration?

8. Suppose additional chloride ions could be added to the AgCl solution in the model. What
would happen to the concentration of the silver ions as a result? Explain.

Problem Solving:
1. What is the solubility of barium sulfate (Ksp = 1.10 X 10-10)? Report your answer in both moles
BaSO4/liter and grams BaSO4/L.

2. A saturated solution of MgF2 contains 1.2 X 10-3 M Mg2+. What is the value of the solublity
product constant (Ksp) for magnesium fluoride?

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Chapter 17: Solubility Equilibria

Model 2: Common Ion Effect on Solubility

Note: Proceed to the Key Questions. Do not fill in these tables until instructed to do so.
Ca(OH)2(s) ⇌ Ca2+ + 2OH- Ksp = 5.5 X 10-6

Beaker 1 Beaker 2
R Ca(OH)2⇌ Ca2+ 2OH -
Ca(OH)2⇌ Ca2+ 2OH-
Initial 1.00 mole 0M 0M Initial 1.00 mole 0M 0.20
(concentration (concentration
not needed) not needed)
C

Beaker 3 Beaker 4
R Ca(OH)2⇌ Ca2+ 2OH -
Ca(OH)2⇌ Ca2+ 2OH-
Initial 1.00 mole 0.20 M 0M Initial 1.00 mole 0M 0.50
(concentration (concentration
not needed) not needed)
C

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Chapter 17: Solubility Equilibria

Key questions.
9. Why is it unnecessary to include the concentration of Ca(OH)2 in the RICE tables?

10. Match each of the following. You may assume that the volume does not change as solid is
added or as solid dissolves.
a. A 1.00 mole sample of solid calcium hydroxide is added to 500.0 mL of water in a
beaker ________________.

b. A 1.00 mole sample of solid calcium hydroxide is added to 500.0 mL of 0.500 M

sodium hydroxide solution in beaker _________________.

c. A 1.00 mole sample of solid calcium hydroxide is added to 500.0 mL of 0.200 M

sodium hydroxide solution in a beaker ________________.

d. A 1.00 mole sample of solid calcium hydroxide is added to 500.0 mL of 0.200 M

calcium nitrate in a beaker ________________.

11. Based on the Ksp for Ca(OH)2, do you expect most of the 1.00 mole sample of solid to
dissolve in any of the four beakers?

12. Three of the beakers in Model 1 contain a common ion in solution.

a. Which beakers in Model 1 contain a common ion?

b. Where does the common ion come from each beaker (refer to question # 10)?

13. Predict what will be in Beakers 1 and 2 when the systems in those beakers reach equilibrium.
Use particulate drawings below to communicate your predictions. You may omit water
molecules for clarity.

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Chapter 17: Solubility Equilibria

14. Write the equation for the solubility product constant, Ksp, for calcium hydroxide.

15. Divide the work among group members to fill in each of the RICE tables in Model 2. Then:
a. Calculate the value of “x” using the Ksp value provided. (There is space below each
RICE table to do your work.
b. Calculate the equilibrium concentration of each ion.
c. What is the solubility of Ca(OH)2 in each beaker? Report your answer in both
moles/liter and grams/liter.

16. What does a large x value mean?

17. Does the presence the presence of a common ion increase or decrease the solubility of the
insoluble salt? Support your answer with evidence from Model 2.

18. According to Model 2, as the concentration of the common ion is increased, how does the
solubility of the insoluble salt change?

19. Are the data and conclusions supported by LeChatlier’s principle? Explain.

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Chapter 17: Solubility Equilibria

Concept Check
Consider the four beakers below. One gram of barium sulfate (BaSO4, Ksp = 1.1 X 10-10), are added to
each beaker. Rank the beakers in terms of solubility of barium sulfate from east soluble to most soluble.
Beaker 1 Beaker 2 Beaker 3 Beaker 4
Water 0.100 M NaCl 0.100 M Na2SO4 0.200 M Ba(NO3)2

Problem Solving:
You try one:
3. The solubility product for silver carbonate, Ag2CO3, is 8.10X10-12. Compare the solubility of
silver carbonate in water to its solubility in a 0.100 M solution of silver nitrate. Support you
comparison with calculations similar to those in Model 2.

Critical Thinking Question:

1. Consider any of the beakers in Model 1. Predict what might happen to the solubility of Ca(OH)2
if a 1.0 M strong acid solution was added drop wise to the beaker?

MODEL 3: The Reaction Quotient and Ksp

We can use the reaction quotient, Z, to determine whether precipitation will occur.
Example: One form of kidney stones is calcium phosphate, Ca3(PO4)2, which has a Ksp of 1.0 X 10-26.
Ca3(PO4)2(s) ⇌3Ca2+(aq) + 2PO43- Qsp= [Ca2+]3 initial [PO43-]2initial Ksp = [Ca2+]3eq [PO43-]2 eq
A sample of urine contains 1.0 X 10-3 M Ca2+and 1.0 X 10-8 M PO43- ion. Is it likely that the patient will
develop kidney stones?
Solution:
Qsp = [1.0 X 10-3]3[1.0 X 10 -8-]2 = 1.0 X10-25 Qsp is GREATER THAN Ksp. The reaction
system will move toward the LEFT (towards the solid). The patient is likely to develop kidney stones.
(Ouch!)

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Chapter 17: Solubility Equilibria

Key Questions:
20. What are the similarities and differences between Qspand Ksp?

21. How is Qsp used to predict whether or not a precipitate will form?

a. If Qsp < Ksp then:

b. If Qsp > Ksp then:

Problem solving: You try one:

4. Will a precipitate form if 0.4 L of 0.500 M Pb(NO3) solution is mixed with 1.6 L of 0.025 M
NaCl solution? (Hint, there is a dilution factor)

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EFFECT OF PH on SOLUBILITY
18.7: Solubility and PH." U.C. Davis- Chemwiki. N.p., 25 Nov. 2013. Web. 23 Apr. 2016.

http://chemwiki.ucdavis.edu/Textbook_Maps/General_Chemistry_Textbook_Maps/Map%3A_General_Chemistry_(Petrucci_et_al.)/18%3A_Solubility_and
_Complex-Ion_Equilibria/18.7%3A_Solubility_and_pH

Skills to Develop: Explain why the solubility of many compounds depends on pH

When the salt dissolves in water, the following reaction occurs:

MA(s)⇌M+(aq)+A−(aq) with Ksp=[M+][A−]

If the salt is BASIC, the anion can also react with water in a hydrolysis reaction:

A−(aq)+H2O(l)⇌OH−(aq)+HA(aq)

What happens to Qsp if we add a strong acid?

Problem:

Consider the salts PbI2 CaF2 and PbSO4

Write the equilibrium reaction and Ksp expression for the solvation of each salt.

PbI2 CaF2 PbSO4

Predict if each salt is acidic or basic. What is the important hydrolysis reaction for each of these salts?

PbI2 CaF2 PbSO4

What effect does adding a strong acid, such as perchloric acid, have on their relative solubilities?

PbI2 CaF2 PbSO4

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Chapter 17: Solubility Equilibria

Fractional or Selective Precipitation (17.3)

Can one type of ion be removed from an aqueous mixture of simple cations by precipitation?
Why? In both industry and research there are often times when on particular component of a mixture
needs to be separated from solution. Maybe it is a rare metal that is dissolved in a mixture of minerals.
Maybe it is a particular protein from lysed plant cells. If the desired component is volatile, distillation
could be used. But if the goal is to separate ions in solution, fractional precipitation is preferred.

1. Consider the experiment setup in Model 1

a. What cations and anions are present in solution A?

b. What is the starting molar concentration of all cations in solution A?

c. Identify the cations and anions present in solution B.

d. What is the concentration of carbonate ions in solution B?

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2. When solution A and solution B mix, there is potential for two precipitates to form. Write double
replacement reactions to show the formation of the two precipitates.
Reaction 1:
Molecular :

Ionic:

Net ionic:

Reaction 2:
Molecular :

Ionic:

Net ionic:

3. In the experiment setup in Model 1, how will the concentration zinc and copper(II) ions be
measured in the experiment?

4. If solution B is added dropwise to solution A, eventually a precipitate will begin to form. What
do you expect to happen to the concentration of either zinc or copper(II) ions as the precipitate
begins to form?

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Concentration of Metal Cations in Solution A

5. Consider the graph in Model 2

a. What is the dependent variable (y-axis)

b. What is the independent variable (x- axis)

c. Why are there two line on the graph? what do the lines represent?

6. Initially there is no change in the concentration of either metal cation in solution A. Explain why
this is the case?

7. According to the graph in Model 2, which precipitate is formed first during the experiment in
Model 1- zinc carbonate or copper(II) carbonate? Justify your reasoning?

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8. Which solute has the higher solubility- zinc carbonate or copper(II) carbonate? Justify your
reasoning.

9. Suppose a researcher wanted to “pull out” as much zinc ion as possible from solution A without
any copper(II) impurity.
a. How many mL of B should the researcher add to solution A?

b. What is the maximum percent of the original zinc ion that could be removed from
solution A without any copper(II) impurity?

10. Suppose a researcher wanted to “pull out” as much copper(II) ion from solution A without any
zinc impurity. Could his be achieved by adding solution B? Explain your reasoning.

11. The solubility product constants for the two precipitates that formed when solution A and solution
B are mixed are 5.4 X 10-11 and 2.5 X 10-10 at 25 0C. Assign these Ksp values to the two
precipitates based on their relative solubilities.

12. Write the Qc and Ksp expressions for both zinc carbonate and copper(II) carbonate in solution. Be
sure to indicate when initial concentrations are being used in the equation and when equilibrium
concentrations ar being used in the equation.

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13. Calculate the initial concentration (before precipitation) of carbonate ions after the addition of
each 0.05 mL of solution B to the 1.00 L beaker of solution A. Divide the work among group
members and write the answers in the table in Model 3. Assume the volume change as solution B
is added is negligible.

14. Notice the initial concentrations of Zn2+ - and Cu2+ in the table in Model 3.
a. Explain how these were obtained from the data in Model 2.

b. As solution B is added and precipitates form, do these initial concentrations change?

15. Use the data in Model 2 to indicate the presence of precipitate (either ZnCO3 or CuCO3) after
each 0.05 mL addition of solution B in Model 3.

16. Use the initial concentrations of carbonate ions and zinc ions to calculate the reaction quotient,
Qsp for the zinc carbonate scenarios in Model 3. Divide the work among group members and
write the answers in the table in Model 3.

17. Use the initial concentrations of carbonate ion and copper(II) ions to calculate the Qsp for the
copper(II) carbonate scenarios in Model 3. Divide the work among group members and write the
answers in the table in Model 3.

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18. Refer to Question 11 for the Ksp value for zinc carbonate and copper(II) carbonate. When a
precipitate forms in solution, how do Qsp and Ksp compare? Use data from Model 3 to support
your answer.

19. Consider the point at which zinc carbonate just begins to precipitate in Model 2.
a. Use the Ksp for zinc carbonate to calculate the concentration of carbonate ions required in
the 1.00 L beaker of solution A precipitate to form.

b. Calculate the volume of solution B that would need to be added to solution A to achieve
the carbonate concentration calculated in part a.

c. Is your answer in part b consistent with the graph in Model 2?

20. Consider the point in the experiment when 0.20 mL of solution B has been added to solution A.
a. Calculate the concentration of carbonate ions in the 1.00 L beaker of solution A at this
point. Consider the volume of solution B negligible.

b. Use the Ksp of zinc carbonate to calculate the concentration of Zn2+ ions remaining in
solution at this point.

c. Is your answer in part b consistent with the graph in Model 2?

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21. Use the of zinc carbonate to calculate the concentration of Zn2+ ions remaining in solution when
copper (II) carbonate begins precipitating. Check your answer against the graph in Model 2.
Hint: Look back at Question 20 for steps on how to solve this question.

Exercises:
1. A solution of 2.00 M sodium sulfide is added drop-wise to a solution that is 2.50 X 10-7 M in both
cobalt(II) ion and nickel(II) ion. The Ksp of cobalt(II) sulfide and nickel(II) sulfide are 5.9 X 10-21
and 3.0 X 10-21, respectively, at 25 0C.
a. Which precipitate will form first when the sodium sulfide is added? Explain your
reasoning.

b. What concentration of sodium sulfide will be required for the first precipitate to form?

c. What concentration of sodium sulfide will be required for the second precipitate to form?

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d. When the second precipitate begins to form, what is the concentration of metal ions that
remains unprecipitated from the first precipitate?

2. A 1.00 M solution of lead(II) nitrate is added drop-wise to 1.00 L of 0.0025 M sodium iodide and
0.0025 M sodium fluoride. The Ksp values of lead(II) iodide and lead(II) fluoride are 8.7 X 10-9
and 3.7 X 10-8, respectively, at 25 0C.
a. Write the solubility product equations for the precipitates that are expected to form.

b. State the initial concentration of I- and F- in the solution.

c. Which precipitate will form first as lead(II) nitrate is added?

d. What volume of lead(II) nitrate will be required for the first precipitate to form?
(Assume the total change in the solution is negligible.)

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e. What volume of lead(II) nitrate will be required for the second precipitate to form?

f. When the second precipitate begins to form, what is the concentration of halide ion that
remains unprecipitated from the first precipitate?

Complex Ion Equilibria (sections 17.5-17.6)

31. Metal ions that form complex ions include Ag+, Cd2+, Cu2+, Fe2+, Fe3+, Ni2+, and Zn2+.

Complexing agents, called ligands, are Lewis bases. Common ligands include:
 CN−  S2O32−
 NH3  OH−.
In each case, an equilibrium is established, called the complex−ion formation equilibrium (Kf)

Ag+(aq) + 2NH3(aq) ⇌ Ag(NH3)2+(aq) Zn2+(aq) + 4OH−(aq) ⇌ Zn(OH)42−(aq)

 2-
[Ag(NH 3 )2 ] [Zn(OH) 4 ]
Kf  Kf 
[Ag ] [NH3 ]2 [Zn 2 ] [OH - ]4
. Questions:
 What is a complex ion?

 What type of metals form complex ions?

 How is the charge on a complex ion determined?

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33.
Write the reaction and Kf expression associated with the first and last complex
ion on the list.

Are Kf values generally large or small?

What does the size of Kf tell you about the position of equilibrium?

Strategies for solving Complex Ion equilibria.

1. First assume that ALL of the metal ion forms a complex ion
a. Look at the size of those Kf values!

2. Solve the dissociation equilibrium

a. Write dissociation equilibrium for the first and last complex ion in table 17.2

b. Write an equilibrium expression and calculate the Kc value for each reaction you wrote in part a.

Example: What is the concentration of Ag+ (aq) ion in 0.00010 M AgNO3 that is also 1.0 M CN?

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Will silver bromide precipitate from a solution containing 0.010 M AgNO3, 0.010 M NaBr, and 1.00 M NH3?
What are the two possible reactions?

Strategy: Begin with the complex ion formation. Why? (The concentration of NH3 is very high. A large
amount of excess reagent helps drive the reaction to completion.)

Now consider the dissociation equilibrium of the complex ion. Write a reaction system and K expression.

Is the concentration of silver ion at this point high enough to precipitate silver bromide?

Calculate the molar solubility of AgBr in 1.0 M NH3 at 25°C. (Ksp for AgBr = 5.0X 10-13; Kf for Ag(NH3)2 is
1.7 X 107)

Strategy:
Write the reaction that occurs between AgBr and NH3 (complex ion formation).

Combine the two equilibria and find the combined equilibrium constant.

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Qualitative analysis of Metal Ions (See lab: Qualitative analysis lab)

PbCl2 is soluble in hot water

How could you separate a mixture of Ag2+, Pb2+, and Cu2+

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