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CHEMFILE MINI-GUIDE TO PROBLEM SOLVING
CHAPTER 22
Equilibrium of Salts, Ksp
When you try to dissolve a solid substance in water, you expect the
solid form to disappear, forming ions or molecules in solution. Most sub-
stances, however, are only slightly soluble in water. For example, when
you stir silver chloride in water, you may think none of the solid dis-
solves. Does this mean that some of the solid dissolves, forms a saturated
solution, and, after that, experiences no further change between the solid
and solution phases? It is true to say that there is no further change in the
amount of substance in either the solution or the solid phase, but to say,
that no further change occurs is inaccurate. An equilibrium exists be-
tween the silver chloride and its dissolved ions, and a state of equilibrium
is a dynamic state. The following chemical equation shows this equilib-
rium.
AgCl(s) N Ag⫹(aq) ⫹ Cl⫺(aq)
Like the other examples of equilibria that you have studied in Chapters
20 and 21, the extent to which this solubility equilibrium proceeds to-
ward the products (the ions in solution) is indicated by an equilibrium
constant. When an equilibrium constant is written for a solubility equilib-
rium, it is called a solubility product constant and is symbolized as Ksp .
In solubility equilibrium problems, the reactants are pure substances,
and pure substances are never included in an equilibrium expression.
That means that you will not have anything in the denominator in the ex-
pression for the solubility product constant. This Ksp expression for the
silver chloride example can be written as follows.
Ksp ⫽ [Ag⫹][Cl⫺]
Note that the coefficients in the balanced equation are understood to be
1 for both silver and chlorine. Therefore, no exponents appear in the Ksp
expression. As with any equilibrium expression, the concentration of
each component is raised to the power of its coefficient from the bal-
anced chemical equation. The value for this solubility product constant is
1.77 ⫻ 10⫺10 at 25°C. The very small value of Ksp indicates that silver
chloride is only very slightly soluble in aqueous solution at this tempera-
ture. The value of Ksp supports the observation that little seems to occur
when silver chloride is stirred into a water solution.
In this chapter, you will learn to apply the solubility equilibrium rela-
tionship to determine Ksp for substances and to calculate concentrations
of ions in saturated solutions using their Ksp values.
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General Plan for Solving Solubility Equilibrium Problems
1
Molarity
of solution
Write the balanced equation
for the dissociation of the
solute.
2
Balanced chemical
equation
Use the mole ratios of
the original solute to
each ion to calculate each
concentration.
3
Concentrations of
If the solution is each ion in solution
saturated, use the Use the balanced
balanced chemical chemical equation to
equation to write the write the ion product
Ksp expression. expression.
4a If Ksp is greater than the ion 4b
Ksp product, the solution is not Ion
expression saturated and no precipitation product
occurs. If Ksp is less than the ion
product, precipitation occurs.
SAMPLE PROBLEM 1
A saturated solution of magnesium fluoride, MgF2 , contains
0.00741 g of dissolved MgF2 per 100. mL at 25°C. What is the
Ksp for magnesium fluoride?
SOLUTION
1. ANALYZE
• What is given in the the mass of MgF2 dissolved in
problem? 100. mL of a saturated solution
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• What are you asked to find? the solubility product constant, Ksp
Items Data
Mass of dissolved MgF2 0.00741 g
Volume of solution 100. mL
Molar mass of MgF2* 62.30 g/mol
Molar concentration of MgF2 ?M
Molar concentration of Mg2ⴙ ?M
ⴚ
Molar concentration of F ?M
Ksp of MgF2
* determined from the periodic table
2. PLAN
• What steps are needed to Determine the molar concentration
calculate the solubility of the saturated MgF2 solution.
product constant, Ksp , Write the balanced chemical equa-
of MgF2? tion for the dissociation of MgF2 ,
and use this equation to de-
termine the concentrations of each
ion in solution. Compute Ksp .
1
Molarity of solution
write a balanced chemical
equation for the dissociation
2
MgF2(s) N Mg2⫹(aq) ⫹ 2F⫺(aq)
use
coefficients
from the
balanced
chemical
equation
3 3
Molarity of Mg2⫹ Molarity of F⫺
use the balanced
equation to write
the Ksp expression,
substitute, and
solve
4a
Ksp ⫽ [Mg2⫹][F⫺]2
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Calculate the molarity of the saturated MgF2 solution.
1
molar mass MgF2
given 1 mol MgF2
g MgF2 ⫻ ⫽ mol MgF2
62.30 g MgF2
given 1L
mL solution ⫻ ⫽ L solution
1000 mL
calculated above
mol MgF2
⫽ [MgF2]
L solution
calculated above
Write the balanced chemical equation for the dissociation to deter-
mine the mole ratios of solute and ions.
MgF2(s) N Mg2⫹(aq) ⫹ 2F⫺(aq)
[MgF2] ⫽ [Mg2⫹]
2[MgF2] ⫽ [F⫺]
Write the Ksp expression.
Ksp ⫽ [Mg2⫹] [F⫺]2
calculated
above
Ksp ⫽ [MgF2](2[MgF2])2
3. COMPUTE
1 mol MgF2
0.007 41 g MgF2 ⫻ ⫽ 1.19 ⫻ 10⫺4 mol MgF2
62.30 g MgF2
1L
100. mL solution ⫻ ⫽ 0.100 L solution
1000 mL
1.19 ⫻ 10⫺4 mol MgF2
⫽ [MgF2] ⫽ 1.19 ⫻ 10⫺3 M
0.100 L solution
[Mg2⫹] ⫽ [MgF2] ⫽ 1.19 ⫻ 10⫺3 M
[F⫺] ⫽ 2[MgF2] ⫽ 2.38 ⫻ 10⫺3 M
Ksp ⫽ [1.19 ⫻ 10⫺3][2.38 ⫻ 10⫺3]2 ⫽ 6.74 ⫻ 10⫺9
4. EVALUATE
• Are the units correct? Yes; Ksp has no units.
• Is the number of significant Yes; the number of significant fig-
figures correct? ures is correct because data were
given to three significant figures.
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• Is the answer reasonable? Yes; the calculation can be approxi-
mated as (1 ⫻ 10⫺3)(2.5 ⫻ 10⫺3)2 ⫽
6 ⫻ 10⫺9, which is of the same
order of magnitude as the calculated
answer.
PRACTICE
1. Silver bromate, AgBrO3, is slightly
soluble in water. A saturated solution is
found to contain 0.276 g AgBrO3 dis-
solved in 150.0 mL of water. Calculate
Ksp for silver bromate. ans: Ksp ⫽ 6.09 ⫻ 10⫺5
2. 2.50 L of a saturated solution of calcium
fluoride leaves a residue of 0.0427 g of
CaF2 when evaporated to dryness.
Calculate the Ksp of CaF2 . ans: Ksp ⫽ 4.20 ⫻ 10⫺11
SAMPLE PROBLEM 2
The Ksp for lead(II) iodide is 7.08 ⴛ 10ⴚ9 at 25°C. What is the
molar concentration of PbI2 in a saturated solution?
SOLUTION
1. ANALYZE
• What is given in the the solubility product constant, Ksp
problem? of PbI2
• What are you asked to find? the concentration of PbI2 in a satu-
rated solution
Items Data
Ksp of PbI2 7.08 ⫻ 10⫺9
Concentration of Pb2ⴙ ?
Concentration of Iⴚ ?
Concentration of PbI2 in solution ?
2. PLAN
• What steps are needed to Write the equation for the dissocia-
calculate the concentration tion of PbI2 . Set up the equation for
of dissolved PbI2 in a satu- Ksp , and compute the concentrations
rated solution? of the ions. Determine the concen-
tration of dissolved solute.
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Write the balanced chemical equation for the dissociation of lead(II)
iodide, PbI2 in aqueous solution.
PbI2(s) N Pb2⫹(aq) ⫹ 2I⫺(aq)
Write the Ksp expression.
Ksp ⫽ [Pb2⫹][I⫺]2
Substitute x for [Pb2⫹]. The balanced equation gives the following
relationship:
2[Pb2⫹] ⫽ [I⫺].
Therefore, [I⫺] ⫽ 2x.
Ksp ⫽ [x][2x]2
Rearrange, and solve for x.
Ksp ⫽ [x][4x2]
Ksp ⫽ 4x3
冪
given
Ksp
x⫽3 ⫽ [Pb2⫹]
4
Relate the substituted value to the unknown solution concentration us-
ing the mole ratio from the original balanced chemical equation. The
mole ratio shows that [Pb2⫹] ⫽ [PbI2].
3. COMPUTE
√
3 7.08 ⫻ 10⫺9
x⫽ ⫽ [Pb2⫹] ⫽ 1.21 ⫻ 10⫺3 M
4
[Pb2⫹] ⫽ [PbI2] ⫽ 1.21 ⫻ 10⫺3 M
4. EVALUATE
• Are the units correct? Yes; concentrations are in molarity
(mol/L).
• Is the number of significant Yes; the number of significant fig-
figures correct? ures is correct because data were
given to three significant figures.
• Is the answer reasonable? Yes; the best check is to use the re-
sult to calculate Ksp and see if it
gives (or is very near) the Ksp you
started with. In this case, the calcu-
lated Ksp is 7.08 ⫻ 10⫺9, the same
value as was given.
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PRACTICE
1. The Ksp of calcium sulfate, CaSO4, is
9.1 ⫻ 10⫺6. What is the molar
concentration of CaSO4 in a
saturated solution? ans: 3.0 ⫻ 10⫺3 M
2. A salt has the formula X2Y, and
its Ksp is 4.25 ⫻ 10⫺7.
a. What is the molarity of a saturated
solution of the salt? ans: [X2Y] ⫽ 4.74 ⫻ 10⫺3 M
b. What is the molarity of a solution
of AZ if its Ksp is the same value? ans: [AZ] ⫽ 6.52 ⫻ 10⫺4 M
SAMPLE PROBLEM 3
Will precipitation of strontium sulfate occur when 50.0 mL
of 0.025 M strontium nitrate solution is mixed with 50.0 mL
of a 0.014 M copper(II) sulfate solution? The Ksp of SrSO4 is
3.2 ⴛ 10ⴚ7.
SOLUTION
1. ANALYZE
• What is given in the the molar concentrations of the
problem? solutions to be mixed, the identities
of the solutes, and the volumes of
the solutions to be mixed
• What are you asked to find? whether a precipitate of strontium
sulfate forms when the two solutions
are mixed
Items Data
Concentration of solution 1 0.025 M SrNO3
Volume of solution 1 50.0 mL
Concentration of solution 2 0.014 M CuSO4
Volume of solution 2 50.0 mL
Volume of combined solution 100.0 mL
Concentration of combined solution ? M SrSO4
Potential precipitate SrSO4
Ksp of SrSO4 3.2 ⫻ 10⫺7
Precipitate/no precipitate forms ?
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2. PLAN
• What steps are needed to Calculate the molar concentrations
determine whether a of the ions that can form a precipi-
precipitate will form? tate in the new volume of solution.
Use these concentrations to calcu-
late the ion product. Compare the
ion product with Ksp .
2
SrSO4(aq) N Sr2⫹(aq) ⫹ SO42⫺(aq)
use the molarity of use the molarity of
Sr(NO3)2, and CuSO4 , and
calculate the calculate the
molarity of Sr 2⫹ in molarity of SO42⫺ in
the new diluted the new diluted
solution solution
3 3
Molarity of Sr2⫹ Molarity of SO42⫺
use coefficients
from the balanced
chemical equation
4a 4b
Ksp ion product ⫽ [Sr2⫹][SO42⫺]
if Ksp ⬍ ion product,
precipitate forms,
if Ksp ⬎ ion product,
no precipitate
forms
Precipitate or
no precipitate
Write the balanced equation for the dissociation of SrSO4 .
SrSO4(aq) N Sr2⫹(aq) ⫹ SO2⫺
4 (aq)
Calculate the molarities of Sr2⫹ and SO2⫺4 . This is a simple dilution
calculation. The subscript 1 in each case represents that individual so-
lution; the subscript 2 represents the combined solution.
Sr(NO3)2(aq) N Sr2⫹(aq) ⫹ 2NO⫺3 (aq)
[Sr ]1 ⫽ [Sr(NO3)2]
2⫹
[Sr2⫹]1V1 ⫽ [Sr2⫹]2V2
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calculated
above given
[Sr2⫹]1 V1
[Sr2⫹]2 ⫽
V2
sum of volumes of
solutions mixed
CuSO4(aq) N Cu2⫹(aq) ⫹ SO2⫺ 4 (aq)
[SO2⫺ ]
4 1 ⫽ [CuSO 4 ]
[SO2⫺ ] V
4 1 1 ⫽ [SO 2⫺
4 2V2
]
calculated
above given
[SO2⫺
4 ]1 V1
4 ]2 ⫽
[SO2⫺
V2
sum of volumes of
solutions mixed
Calculate the ion product for SrSO4 .
calculated
above
ion product ⫽ [Sr 2⫹
]2 [SO2⫺
4 ]2
Compare the ion product to the Ksp value to determine if precipitation
occurs.
3. COMPUTE
0.025 M ⫻ 50.0 mL
[Sr2⫹]2 ⫽ ⫽ 1.2 ⫻ 10⫺2 M
100.0 mL
⫺ 0.014 M ⫻ 50.0 mL
[SO 42 ]2 ⫽ ⫽ 7.0 ⫻ 10⫺3 M
100.0 mL
ion product ⫽ [1.2 ⫻ 10⫺2][7.0 ⫻ 10⫺3] ⫽ 8.4 ⫻ 10⫺5
Ksp ⫽ 3.2 ⫻ 10⫺7
Ksp ⬍ ion product
Precipitation will occur.
4. EVALUATE
• Are the units correct? Yes; the ion product has no units.
• Is the number of significant Yes; the number of significant fig-
figures correct? ures is correct because data were
given to a minimum of two signifi-
cant figures.
• Is the answer reasonable? Yes; the calculation can be approxi-
mated as 0.01 ⫻ 0.007 ⫽
0.000 07 ⫽ 7 ⫻ 10⫺5, which is of
the same order of magnitude as the
calculated result.
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PRACTICE
In each of the following problems, include the calculated ion product
with your answer.
1. Will a precipitate of Ca(OH)2
form when 320. mL of a
0.046 M solution of NaOH
mixes with 400. mL of
a 0.085 M CaCl2 solution? ans: ion product ⫽ 1.9 ⫻ 10⫺5
⫺6
Ksp of Ca(OH)2 is 5.5 ⫻ 10 . precipitation occurs
2. 20.00 mL of a 0.077 M solu-
tion of silver nitrate, AgNO3 ,
is mixed with 30.00 mL of a
0.043 M solution of sodium
acetate, NaC2H3O2 . Does a
precipitate form? The Ksp of ans: ion product ⫽ 8.1 ⫻ 10⫺4
⫺3
AgC2H3O2 is 2.5 ⫻ 10 . no precipitate
3. If you mix 100. mL of
0.036 M Pb(C2H3O2)2 with
50. mL of 0.074 M NaCl,
will a precipitate of PbCl2
form? Ksp of PbCl2 is ans: ion product ⫽ 1.5 ⫻ 10⫺5
⫺4
1.9 ⫻ 10 . no precipitate
4. If 20.00 mL of a 0.0090 M
solution of (NH4)2S is mixed
with 120.00 mL of a 0.0082 M
solution of Al(NO3)3 , does a
precipitate form? The Ksp ans: ion product ⫽ 1.1 ⫻ 10⫺13
⫺7
of Al2S3 is 2.00 ⫻ 10 . no precipitate
ADDITIONAL PROBLEMS
1. The molar concentration of a saturated calcium chromate, CaCrO4 ,
solution is 0.010 M at 25°C. What is the Ksp of calcium chromate?
2. A 10.00 mL sample of a saturated lead selenate solution is found to
contain 0.00136 g of dissolved PbSeO4 at 25°C. Determine the Ksp
of lead selenate.
3. A 22.50 mL sample of a saturated copper(I) thiocyanate, CuSCN,
solution at 25°C is found to have a 4.0 ⫻ 10⫺6 M concentration.
a. Determine the Ksp of CuSCN.
b. What mass of CuSCN would be dissolved in 1.0 ⫻ 103 L of
solution?
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4. A saturated solution of silver dichromate, Ag2Cr2O7 , has a concen-
tration of 3.684 ⫻ 10⫺3 M. Calculate the Ksp of silver dichromate.
5. The Ksp of barium sulfite, BaSO3 , at 25°C is 8.0 ⫻ 10⫺7 .
a. What is the molar concentration of a saturated solution of
BaSO3 ?
b. What mass of BaSO3 would dissolve in 500. mL of water?
6. The Ksp of lead(II) chloride at 25°C is 1.9 ⫻ 10⫺4. What is the
molar concentration of a saturated solution at 25°C?
7. The Ksp of barium carbonate at 25°C is 1.2 ⫻ 10⫺8.
a. What is the molar concentration of a saturated solution of
BaCO3 at 25°C?
b. What volume of water would be needed to dissolve 0.10 g of
barium carbonate?
8. The Ksp of SrSO4 is 3.2 ⫻ 10⫺7 at 25°C.
a. What is the molar concentration of a saturated SrSO4 solution?
b. If 20.0 L of a saturated solution of SrSO4 were evaporated to
dryness, what mass of SrSO4 would remain?
9. The Ksp of strontium sulfite, SrSO3 , is 4.0 ⫻ 10⫺8 at 25°C. If
1.0000 g of SrSO3 is stirred in 5.0 L of water until the solution is
saturated and then filtered, what mass of SrSO3 would remain?
10. The Ksp of manganese(II) arsenate is 1.9 ⫻ 10⫺11 at 25°C. What is
the molar concentration of Mn3(AsO4)2 in a saturated solution? Note
that five ions are produced from the dissociation of Mn3(AsO4)2 .
11. Suppose that 30.0 mL of a 0.0050 M solution of Sr(NO3)2 is mixed
with 20.0 mL of a 0.010 M solution of K2SO4 at 25°C. The Ksp of
SrSO4 is 3.2 ⫻ 10⫺7.
a. What is the ion product of the ions that can potentially form a
precipitate?
b. Does a precipitate form?
12. Lead(II) bromide, PbBr2 , is slightly soluble in water. Its Ksp is
6.3 ⫻ 10⫺6 at 25°C. Suppose that 120. mL of a 0.0035 M solution
of MgBr2 is mixed with 180. mL of a 0.0024 M Pb(C2H3O2)2 solu-
tion at 25°C.
a. What is the ion product of Br⫺ and Pb2⫹ in the mixed solution?
b. Does a precipitate form?
13. The Ksp of Mg(OH)2 at 25°C is 1.5 ⫻ 10⫺11 .
a. Write the equilibrium equation for the dissociation of Mg(OH)2 .
b. What volume of water would be required to dissolve 0.10 g of
Mg(OH)2 ?
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c. Considering that magnesium hydroxide is essentially insoluble,
why is it possible to titrate a suspension of Mg(OH)2 to an
equivalence point with a strong acid such as HCl?
14. Lithium carbonate is somewhat soluble in water; its Ksp at 25°C is
2.51 ⫻ 10⫺2 .
a. What is the molar concentration of a saturated Li2CO3 solution?
b. What mass of Li2CO3 would you dissolve in order to make
3440 mL of saturated solution?
15. A 50.00 mL sample of a saturated solution of barium hydroxide,
Ba(OH)2 , is titrated to the equivalence point by 31.61 mL of a
0.3417 M solution of HCl. Determine the Ksp of Ba(OH)2 .
16. Calculate the Ksp for salts represented by QR that dissociate into two
ions, Q⫹ and R⫺, in each of the following solutions:
a. saturated solution of QR is 1.0 M
b. saturated solution of QR is 0.50 M
c. saturated solution of QR is 0.1 M
d. saturated solution of QR is 0.001 M
17. Suppose that salts QR, X2Y, KL2 , A3Z, and D2E3 form saturated so-
lutions that are 0.02 M in concentration. Calculate Ksp for each of
these salts.
18. The Ksp at 25°C of silver bromide is 5.0 ⫻ 10⫺13. What is the molar
concentration of a saturated AgBr solution? What mass of silver
bromide would dissolve in 10.0 L of saturated solution at 25°C?
19. The Ksp at 25°C for calcium hydroxide is 5.5 ⫻ 10⫺6.
a. Calculate the molarity of a saturated Ca(OH)2 solution.
b. What is the OH⫺ concentration of this solution?
c. What is the pH of the saturated solution?
20. The Ksp of magnesium carbonate is 3.5 ⫻ 10⫺8 at 25°C. What mass
of MgCO3 would dissolve in 4.00 L of water at 25°C?
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