Chapter 17

Practice Exercises
17.1

Ba3(PO4)2(s) U 3Ba2+(aq) + 2PO43+(aq)

Ksp = [Ba2+]3[PO43+]2

17.2

(a)

17.3

TlI(s) U Tl+(aq) + I(aq)

Ksp = [Tl+][I]
1 mol TlI
5
mol TlI = 5.9 103 g
= 1.78 10 mol TlI
331.3
g
TlI

Ksp = [Ba2+][C2O42]

(b)

Ksp = [Ag+]2[SO42]

1.78 105 mol

= 1.78 105 M
1L
Ksp = (1.8 105)(1.8 105) = 3.2 1010

[Tl+] = [I] =

17.4

)( (

K sp = 2.15 103 2 2.15 103

17.5

K sp = Pb 2+ F

PbF2(s) U Pb2+(aq) + 2F(aq)

))

= 3.98 108

Ag2SO4(s) U 2Ag+(aq) + SO42(aq)

1 mol Na 2SO4
Mol Na2SO4 added = (28.4 g Na2SO4)
= 0.200 mol Na2SO4
142.04 g Na 2SO 4

Concentration of SO42 =

I
C
E

0.200 mol SO42

= 0.200 M SO42
1 L solution

[Ag+]

+ (4.3 103) 2
+ 8.6 103

[SO42]
0.200
+ 4.3 103
0.200 + 4.3 103

Ksp = [Ag+]2[SO42]
Ksp (8.6 103)2(0.204) = 1.5 105
17.6

CoCO3(s) U Co2+(aq) + CO32(aq)

I
C
E

[Co2+]

+1.0 109
+1.0 109

[CO32]
0.10
+ 1.0 109
0.10 + 1.0 109

Substituting the above values for equilibrium concentrations into the expression for Ksp gives:
Ksp = [Co2+][CO32] = (1.0 109)(0.10 + 1.0 109) = 1.0 1010

397

Chapter 17
17.7

PbF2(s) U Pb2+(aq) + 2F(aq)

I
C
E

[Pb2+]
0.10
+ 3.1 104
0.10 + (3.1 104)

[F]

+ 2(3.1 104)
+ 6.2 104

Substituting the above values for equilibrium concentrations into the expression for Ksp gives:
Ksp = [Pb2+][F]2 = [0.10 + 3.1 104][6.2 104]2
Now (0.10 + 3.1 104) is also 0.10:
Hence, Ksp = (0.10)(6.2 104)2 = 3.9 108
17.8

Ag3PO4(s) U 3Ag+(aq) + PO43+(aq)

Ksp = [Ag+]3[PO43+] = 2.8 1018
I
C
E

[Ag+]

+ 3x
+ 3x

[PO43+]

+x
+x

Ksp = [3x]3[x] = 2.8 1018

2.8 1018 = 27x4
x4 = 1.04 1019
x = 1.04 1019
x = 1.79 105
Thus the solubility is 1.8 105 M Ag3PO4.
4

17.9

(a)

AgBr(s) U Ag+(aq) + Br(aq)

I
C
E

[Ag+]

+x
+x

Ksp = [Ag+][Br] = 5.0 1013

[Br]

+x
+x

Substituting the above values for equilibrium concentrations into the expression
for Ksp gives:
Ksp = 5.0 1013 = [Ag+][Br] = (x)(x)

x = 5.0 1013 = 7.1 107

Thus the solubility is 7.1 107 M AgBr.
(b)

Ag2CO3(s) U 2Ag+(aq) + CO32(aq)

I
C
E

[Ag+]

+ 2x
+ 2x

Ksp = [Ag+]2[CO32] = 8.1 1012

[CO32]

+x
+x

Substituting the above values for equilibrium concentrations into the expression for Ksp gives:
Ksp = 8.1 x 1012 = [Ag+]2[CO32] = (2x)2(x) and 4x3 = 8.1 1012

398

Chapter 17

x = 3 8.1 1012 / 4 = 1.3 104

Thus the molar solubility is 1.3 104 M Ag2CO3.

17.10

AgI(s) U Ag+(aq) + I(aq)

Ksp = [Ag+][I] = 8.3 1017

The initial concentration of I is 2 0.20 M from the CaI2.

I
C
E

[Ag+]

+x
+x

[I]
0.40
+x
0.40 + x

Substituting the above values for equilibrium concentrations into the expression for Ksp gives:
Ksp = 8.3 1017 = [Ag+][I] = (x)(0.40 + x)
We know that the value of Ksp is very small, and it suggests the simplifying assumption that
(0.40 + x) 0.40:
Hence, 8.3 1017 = (0.40)x, and x = 2.1 1016.
The assumption that
(0.40 + x) 0.40 is seen to be valid indeed.
Thus 2.1 1016 M of AgI will dissolve in a 0.20 M CaI2 solution.
In pure water,
Ksp = 8.3 1017 = [Ag+][I] = (x)(x)
x = [AgI(aq)] = 9.1 109 M (much more soluble)
17.11

Fe(OH)3(s) U Fe3+(aq) + 3OH(aq)

I
C
E

[Fe3+]

+x
+x

Ksp = [Fe3+][OH]3 = 1.6 1039

[OH]
0.050
+ 3x
0.050 + 3x

Substituting the above values for equilibrium concentrations into the expression for Ksp gives:
Ksp = 1.6 1039 = [Fe3+][OH]3 = (x)[0.050 + 3x]3
We try to simplify by making the approximation that (0.050 + 3x) 0.050:
1.6 1039 = (x)(0.050)3 or x = 1.3 1035
Clearly the assumption that (0.050 + 3x) 0.050 is justified.
Thus 1.3 1035 M of Fe(OH)3 will dissolve in a 0.050 M sodium hydroxide solution.
17.12

The expression for Ksp is Ksp = [Ca2+][SO42] = 2.4 105 and the ion product for this solution would be:
[Ca2+][SO42] = (2.5 103)(3.0 102) = 7.5 105
Since the ion product is larger than the value of Ksp, a precipitate will form.

17.13

The solubility product constant is Ksp = [Ag+]2[CrO42] = 1.2 1012 and the ion product for this solution
would be:
[Ag+]2[CrO42] = (4.8 105)2(3.4 104) = 7.8 1013
Since the ion product is smaller than the value of Ksp, no precipitate will form.

399

Chapter 17
We expect PbSO4(s) since nitrates are soluble.

17.14

Because two solutions are to be mixed together, there will be a dilution of the concentrations of the various
ions, and the diluted ion concentrations must be used. In general, on dilution, the following relationship is
found for the concentrations of the initial solution (Mi) and the concentration of the final solution (Mf):
MiVi = MfVf
Thus the final or diluted concentrations are:
Pb 2+ = 1.0 103 M 100.0 mL = 5.0 104 M
200.0 mL

SO 2 = 2.0 103 M 100.0 mL = 1.0 103 M

200.0 mL
4

The value of the ion product for the final (diluted) solution is:
[Pb2+][SO42] = (5.0 104)(1.0 103) = 5.0 107
Since this is smaller than the value of Ksp (6.3 107), a precipitate of PbSO4 is not expected.
17.15

We expect a precipitate of PbCl2 since nitrates are soluble.

We proceed as in Practice Exercise 14. MiVi = MfVf
Pb 2+ = ( 0.10 M ) 50.0 mL = 0.071 M
70.0 mL

Cl = ( 0.040 M ) 20.0 mL = 0.011 M

70.0 mL

The value of the ion product for such a solution would be:
[Pb2+][Cl]2 = (7.1 102)(1.1 102)2 = 8.6 106
Since the ion product is smaller than Ksp (1.7 105), a precipitate of PbCl2 is not expected.
17.16

CoS will precipitate if the H+ concentration is too low. Solving for Q and then comparing Q to Kspa, we can
determine whether or not CoS will precipitate.
K spa =
Q=

[Co 2+ ][H 2S]

+ 2

[H ]

[Co

2+

][H 2S]

+ 2

[H ]

= 5 101
[0.005][0.10]
[3.16 104 ]2

= 5 103

Q > Kspa
Since Q is greater than Kspa, then the reaction will move to reactants and CoS solid will form.
17.17

Consulting Table 17.2, we find that Fe2+ is much more soluble in acid than Hg2+. We want to make the H+
concentration large enough to prevent FeS from precipitating, but small enough that HgS does precipitate.
First, we calculate the highest pH at which FeS will remain soluble, by using Kspa for FeS. (Recall that a
saturated solution of H2S = 0.10 M.)
K spa =

[Fe2+ ][H 2S]

+ 2

[H ]
[H+] = 0.0013 M
pH = log [H+] = 2.9

[0.010][0.10]
+ 2

[H ]

= 6 102

400

Chapter 17
Since Fe2+ is much more soluble in acid than Hg2+ we already know that this pH will precipitate HgS, but
we can check it by using Kspa for HgS:
K spa =

[Hg 2+ ][H 2S]

+ 2

[H ]
[H+] = 2.2 1014 M

[0.010][0.10]
+ 2

[H ]

= 2 1032

(This concentration is impossibly high, but it tells us that this much acid would be required to dissolve HgS
at these concentrations.)
17.18

BaC2O4(s) U Ba2+(aq) + C2O42(aq)

[Ba2+] = 0.050 M
1.2 107 = (0.050)[C2O42]
[C2O42] = 2.4 106 M
H2C2O4 U H+ + HC2O4
HC2O4 U H+ + C2O42
H2C2O4 U 2H+ + C2O42
[H2C2O4] = 0.10
[C2O42] = 2.4 106 M

Ka1 = 5.6 102

Ka2 = 5.4 105
Ka = (5.4 105) (5.6 102) = 3.0 106

Ka = 3.0 10

Ksp = 1.2 107 = [Ba2+][C2O42]

H + C2 O42
H + 2.4 106

=
=
( 0.10 )
[ H 2 C2 O 4 ]

Since the amount of oxalate formed is so small, the concentration of oxalic acid is essentially unchanged.
[H+] = 3.55 101
This is the minimum concentration of H+ that will prevent the formation of BaC2O4 precipitate.
17.19

Follow the exact procedure outlined in Example 17.10.

Ksp = [Ca2+][CO32]= 4.5 109
Ksp = [Ni2+][CO32] = 1.3 107
NiCO3 is more soluble and will precipitate when:
K sp
1.3 10 7
[CO32] =
=
= 1.3 10 6
0.10
[Ni 2+ ]
CaCO3 will precipitate when:
K sp
4.5 10
=
[CO32 ] =
2+
0.10
[Ca ]

= 4.5 10 8

CaCO3 will precipitate and NiCO3 will not precipitate if [CO32] > 4.5 108 and [CO32] < 1.3 106.
Now, using the equation in example 17.10 we get:
0.030

[H + ]2 = (2.4 1017 )
[CO 2 ]
3

NiCO3 will precipitate if:

0.030
[H + ]2 = (2.4 1017 )
= 5.5 1013
6
1.3 10
pH = 6.13
[H+] = 7.4 107

401

Chapter 17
CaCO3 will precipitate:
0.030
11
[H + ]2 = (2.4 1017 )
= 1.6 10
4.5 108
[H + ] = 4.0 106

pH = 5.40

So CaCO3 will precipitate and NiCO3 will not if the pH is maintained between pH = 5.40 and pH = 6.13
17.20

The overall equilibrium is AgCl(s) + 2NH3(aq) U Ag(NH3)2+(aq) + Cl(aq)

Ag(NH3 ) 2+ Cl

Kc =
2
NH
3

In order to obtain a value for Kc for this reaction, we need to use the expressions for Ksp of AgCl(s) and the
Kform of Ag(NH3)2+:
K sp = Ag + Cl = 1.8 1010

Ag(NH ) +
3 2
K form =
= 1.6 107
2
+
Ag NH

3
K c = K sp K form

Ag(NH ) + Cl
3 2
= 2.9 103
=
2
NH3

Now we may use an equilibrium table for the reaction in question:

I
C
E

[Ag(NH3)2+]

+x
x

[NH3]
0.10
2x
0.10 2x

[Cl]

+x
x

Substituting these values into the mass action expression gives:

K c = 2.9 103 =

(x)(x)
(0.10 2x)2

(x)
(0.10 2x)
Solving for x we get, x = 4.9 103 M. The molar solubility of AgCl in 0.10 M
NH3 is therefore 4.9 103 M.

Take the square root of both sides to get 0.054 =

In order to determine the solubility in pure water, we simply look at Ksp

AgCl(s) U Ag+ (aq) + Cl(aq)

Ksp = [Ag+][Cl] = 1.8 1010

At equilibrium; [Ag+] = [Cl] = 1.3 105. Hence the molar solubility of AgCl in 0.10 M NH3 is about 380
times greater than in pure water.

402

Chapter 17
17.21

We will use the information gathered for the last problem. Specifically,
AgCl(s) + 2NH3(aq) U Ag(NH3)2+(aq) + Cl(aq)
Ag(NH3 ) 2+ Cl

= 2.9 103
Kc =
2
NH3

If we completely dissolve 0.20 mol of AgCl, the equilibrium [Cl] and [Ag(NH3)2+] will be 0.20 M in a one
liter container. The question asks, therefore, what amount of NH3 must be initially present so that the
equilibrium concentration of Cl is 0.20 M?
[NH3]
Z
2x
Z 2x

I
C
E
K c = 2.9 103 =

[Ag(NH3)2+]

+x
x

[Cl]

+x
x

(x)(x)

(Z 2x) 2
Take the square root of both sides to get;
x
0.20
0.054 =
=
Z 2x
Z 0.40

We have substituted the known value of x. Solving for Z we get, Z = 4.1 M

Consequently, we would need to add 4.1 moles of NH3 to a one liter container of 0.20 M AgCl in order to
completely dissolve the AgCl.
Review Questions
17.1

The ion product is the quantity which results from the mass action expression and it is a product of the ion
concentrations. The ion product constant, also called the solubility product constant, is equal to the product
of the ion concentrations for a saturated solution of a sparingly soluble substance.

17.2

The addition of a common ion to a saturated solution lowers the solubility of a sparingly soluble ionic salt.
According to Le Chteliers principle, addition of an ion to a saturated solution will shift the equilibrium so
as to absorb as much of the added ion as possible. This results in the precipitation of the sparingly soluble
salt. In the case of AgCl, Ksp = 1.8 1010, addition of NaCl to a saturated solution containing Ag+ and Cl
will result in the precipitation of AgCl(s). The common ion in this case is Cl. It is present in the solution
due to the NaCl as well as the AgCl.
3

17.3

Ba 2+ PO 3
4
Kc =
Ba 3 ( PO4 )
2

The denominator of the mass action expression is a constant since the concentration of substance within a
pure solid is constant. Consequently, we define a new constant which is the product of Kc and the
concentration of the pure solid.
3

K sp = Ba 2+ PO43

17.4

When the value of the ion product is greater than Ksp, a precipitate will form.

403

Chapter 17
17.5

Ksp values assume 100% dissociation of the ions, but in solution, the ions are not fully dissociated, but
instead ion pairs are often formed.

17.6

When sodium acetate is added to a solution of acetic acid, the equilibrium is disrupted and more acetic acid
is formed. This lowers the amount of hydronium ions in solution thus raising the pH.

17.7

Na2S(s) U 2Na+(aq) + HS(aq) + OH(aq)

17.8

The oxide ion reacts with the water to produce hydroxide ion: O2 + H2O J 2OH

17.9

As the pH of an oxalic acid solution is decreased, the hydrogen ion concentration is increased, this shifts
the equilibrium to the undissociated acid, thus increasing the H2C2O4 concentration. The opposite is true as
the pH of the solution is increased.

17.10

By combining the three dissociation expressions for phosphoric acid, we come up with a single expression
that relates the hydrogen ion concentration and the phosphate ion concentration:
H3PO4(aq) U 3H+(aq) + PO43(aq)
K = K a1 K a2 K a3

17.11

(a)
(b)

17.12

CoS(s) U Co2+(aq) + HS(aq) + OH(aq)

+

2+

CoS(s) + 2H (aq) U Co (aq) + H2S(aq)

Ksp = [CO2+][HS][OH]
Co 2+ [ H 2S]

K spa =
2
H+

NH3(aq) + H2O U NH4+(aq) + OH(aq)

The addition of NH4Cl to the mixture of Mg(OH)2 and water causes the Mg(OH)2 to dissolve because the
NH4+ reacts with the OH and shifts the equilibrium towards the dissolution of the solid.

17.13

AgCl(s) U Ag+(aq) + Cl(aq)

Ag+(aq) + 2NH3(aq) U Ag(NH3)2+(aq)
Silver chloride is an insoluble solid. However, any Ag+ ions present react with added NH3 to form the
Ag(NH3)2+ complex ion. According to Le Chteliers Principle, as NH3 is added to a solution containing
Ag+ ions, the complex ion forms using up the Ag+ ions. This disrupts the equilibrium and forces AgCl to
dissolve.
Upon addition of HNO3, a strong acid, H+ reacts with NH3 to form NH4+. This disrupts the complex
equilibria and causes the Ag(NH3)2+ to dissociate and form free Ag+ ions. Once again, the [Ag+] reaches a
value sufficient in the presence of Cl to precipitate AgCl in accordance with Le Chteliers Principle.

17.14

AgCl and AgBr are both insoluble compounds. However, AgBr is less soluble than AgCl. When solid
AgCl is added to an aqueous solution of MgBr2, some of the AgCl dissociates. The Ag+ ion reacts with the
aqueous Br to form insoluble AgBr. This disrupts the AgCl/Ag+ equilibrium and additional AgCl
dissociates. With sufficient stirring, and perhaps a little heat, all of the AgCl will dissolve and AgBr will
precipitate.

404

Chapter 17
17.15

PbCl2(s) U Pb2+(aq) + 2Cl(aq)

Pb2+(aq) + 3Cl(aq) U PbCl3(aq)
mol PbCl

volume

K form =

PbCl
3

Pb 2+ Cl

K form = ( volume )

mol Pb 2+
mol Cl

volume
volume

( mol PbCl )
( mol Pb )( mol Cl )
3

2+

Notice that the above expression is the product of a ratio of mole amounts and a volume3 term. The
constant Kform does not change on dilution, but the volume term is changed by dilution. This means that the
ratio of moles term in the above expression must change on dilution, in order to hold the product constant.
If the volume is doubled, the ratio of moles would have to become smaller by a factor of 8 (= 23) in order
for the entire argument to have a constant value, i.e, in order for Kform to remain constant on dilution.
This means that the concentrations of Pb2+ and Cl must increase as the solution containing the complex ion
is diluted. Eventually the ion product for PbCl2 will exceed the value of Ksp for PbCl2, resulting in its
precipitation.
Review Problems
17.16

(a)
(b)
(c)
(d)
(e)
(f)

CaF2(s) U Ca2+ + 2F
Ag2CO3(s) U 2Ag+ + CO32
PbSO4(s) U Pb2+ + SO42
Fe(OH)3(s) U Fe3+ + 3OH
PbI2(s) U Pb2+ + 2I
Cu(OH)2(s) U Cu2+ + 2OH

Ksp = [Ca2+][F]2
Ksp = [Ag+]2[CO32]
Ksp = [Pb2+][SO42]
Ksp = [Fe3+][OH]3
Ksp = [Pb2+][I]2
Ksp = [Cu2+][OH]2

17.17

(a)
(b)
(c)
(d)
(e)
(f)

AgI(s) U Ag+ + I
Ag3PO4(s) U 3Ag+ + PO43
PbCrO4(s) U Pb2+ + CrO42
Al(OH)3(s) U Al3+ + 3OH
ZnCO3(s) U Zn2+ + CO32
Zn(OH)2(s) U Zn2+ + 2OH

Ksp = [Ag+][I]
Ksp = [Ag+]3[PO43]
Ksp = [Pb2+][CrO42]
Ksp = [Al3+][OH]3
Ksp = [Zn2+][CO32]
Ksp = [Zn2+][OH]2

17.18

BaSO3(s) U Ba2+ + SO32

Ksp = [Ba2+][SO32]
6
7
Ksp = (0.10)(8.0 10 ) = 8.0 10
In this problem, all of the Ba2+ comes from the BaCl2.

17.19

To solve this problem we need to realize that the concentration of the solution is equal to the number of
moles of solid recovered divided by the volume of the solution, i.e.,
0.649 g CaCrO 1 mole CaCrO 1000 mL
[CaCrO4 ] = 156 mL 4 156.1 g CaCrO4 1 L = 0.0267 M

4
The equilibrium for this problem is CaCrO4(s) U Ca2+ + CrO42
Ksp = [Ca2+][CrO42] = (0.0267)2 = 7.13 104

405

Chapter 17
17.20

PbCl2 U Pb2+ + 2Cl

Ksp = [Pb2+][Cl]2
2+

At equilibrium [Pb ] = 0.016 M and [Cl ] = 0.032 M

so Ksp = (0.016)(0.032)2 = 1.6 105

17.21

Ksp = [Ba2+][F]-2
BaF2 U Ba2+(aq) + 2F(aq)
First find the concentration of the Ba2+ and F that was in solution and then find the value for Ksp.
Using the amount of BaF2 recovered; determine the number of moles of each ion, then find the
concentration of each ion.
1 mol BaF2
4
mole BaF2 = 0.132 g BaF2
= 7.53 10 mol BaF2
175.32
g
BaF
2

4
7.53 10 mol BaF 1 mol Ba 2+ 1000 mL
2
= 7.53 103 M Ba2+
[Ba2+] =

100 mL solution
1 mol BaF2 1 L

7.53 104 mol BaF 2 mol F 1000 mL

2
[F] =
= 1.51 102 M F

100 mL solution
1 mol BaF2 1 L

Ksp = [Ba2+][F] = (7.53 103)(1.51 102)2 = 1.7 106

17.22

Ag3PO4(s) U 3Ag+ + PO43

Ksp = [Ag+]3[PO43]
5 3
5
Ksp = [3(1.8 10 )] [1.8 10 ] = 2.8 1018

17.23

Ba3(PO4)2(s) U 3Ba2+ + 2PO43 Ksp = [Ba2+]3[PO43]2

Ksp = [3(1.4 108)]3[2(1.4 108)]2 = 5.8 1038

17.24

1 mole BaSO4
5
mol BaSO4 = ( 0.00245 g BaSO 4 )
= 1.05 10 mol
233.3906 g BaSO 4
[Ba2+] = [SO42] = 1.05 105 M

Ksp = [Ba2+][SO42] = (1.05 105)2 = 1.10 1010

17.25

1 mol AgC2 H3O 2

3
mol AgC2 H3O2 = ( 0.800 g AgC2 H3O 2 )
= 4.79 10 mol AgC2 H3O2
166.9
g
AgC
H
O
2 3 2

4.79 103 mol AgC2 H3O2

= 4.79 102 M
0.100 L solution
One mole of Ag+ and one mole of C2H3O2 will be produced for every mole of AgC2H3O2. Therefore,
Ksp = [Ag+][C2H3O2] = (4.79 102)2 = 2.29 103.

[AgC2H3O2] =

17.26

For every mole of CO32 produced, 2 moles of Ag+ will be produced. Let x = [CO32] at equilibrium and
[Ag+] = 2x at equilibrium. Ksp = [Ag+]2[CO32] = 8.1 1012 = (2x)2(x) = 4x3. Solving we find x = 1.3
104. Thus, the molar solubility of Ag2CO3 is 1.3 104 moles/L.

17.27

For every mole of Pb2+ produced, 2 moles of F will be produced.

Let x = [Pb2+] at equilibrium and [F] = 2x at equilibrium.
Ksp = [ Pb2+][F]2 = 3.6 108 = (x)(2x)2 = 4x3.
Solving we find x = 2.1 103 M.
Thus, the molar solubility of PbF2 is 2.1 103 moles/L.

406

Chapter 17
17.28

PbBr2(s) U Pb2+ + 2Br

I
C
E

[Pb2+]

+x
+x

Ksp = [Pb2+][Br]2
[Br]

+ 2x
+ 2x

Ksp = (x)(2x)2 = 4x3 = 2.1 106, x =

17.29

2.1 106
= 8.1 103 M
4

Ag2CrO4(s) U 2Ag+ + CrO42

I
C
E

[Ag+]

+ 2x
+ 2x

Ksp = [Ag+]2[CrO42]

[CrO42]

+x
+x

Ksp = (2x)2(x) = 4x3 = 1.2 1012, x =

17.30

1.2 1012
= 6.7 105 M
4

First determine the molar solubility of the MX salt.

Ksp = [M+][X] = (x)(x) = 3.2 1010
Let x = [M+] = [X],
5
x = 1.8 10 M. This is the equilibrium concentration of the two ions.
For the MX3 salt, let x = equilibrium concentration of M3+, [X] = 3x.
Ksp = [M+][X]3 = (x)(3x)3 = 27x4. The value of x in this expression is the value determined in the first part
of this problem.
So, Ksp = (27)(1.8 105)4 = 2.8 1018

17.31

First determine the molar solubility of the M2X3 salt.

M2X3 (s) U 2M3+ (aq) + 3X2(aq)
Ksp = [M3+]2[X2]3

I
C
E

[M3+]

+ 2x
+ 2x

[X2]

+ 3x
+ 3x

Ksp = (2x)2(3x)3= 2.2 1020 = 108x5

x = 4.6 105 M
The molar solubility of this compound is 4.6 105 moles/L
We want the molar solubility of the M2X compound to be twice the value just calculated or 9.2 105
moles/L. We need to solve the equilibrium expression:
M2X (s) U 2M+ (aq) + X2(aq)

I
C
E

[M+]

+ 2x
+ 2x

Ksp = [M+]2[X2]

[X2]

+x
+x

Ksp = (2x)2(x) = 4x3

So, Ksp = 4(9.2 105)3 = 3.1 1012

where x = 9.2 105 M

407

Chapter 17
17.32

To solve this problem, determine the molar solubility for each compound.
LiF:
let x = [Li+] = [F]
Ksp = [Li+][F] = x2 = 1.7 103
2
x = 4.1 10 moles/L = molar solubility of LiF.
[F]2 = 2x
Ksp = [Ba2+][F]2 = (x)(2x)2 = 1.7 106
BaF2: let x = [Ba2+];
3
6
3
4x = 1.7 10 , and x = 7.5 10 M = molar solubility of BaF2.
Because the molar solubility of LiF is greater than the molar solubility of BaF2, LiF is more soluble.

17.33

To solve this problem, first determine the molar solubility for each compound.
AgCN: let x = [Ag+] = [CN]
Ksp = [Ag+][CN] = x2 = 2.2 1016
8
x = 1.5 10 moles/L = molar solubility of AgCN. The number of grams of AgCN that will dissolve in
100 mL is;
1.5 108 moles 133.9 g
g =
(100 mL) = 2.0 107 g

1 mole
1000
mL

Ksp = [Zn2+][CN]2 = (x)(2x)2 = 3 1016

Zn(CN)2: let x = [Zn2+], [CN] = 2x;
3
16
6
4x = 3 10 , and x = 4.2 10 M = molar solubility of Zn(CN)2. The number of grams of Zn(CN)2
that will dissolve in 100 mL is;
4.2 106 moles 117.4 g
g =
(100 mL) = 4.9 105 g

1 mole
1000
mL

More Zn(CN)2 will dissolve in 100 mL of water so it has the larger solubility.
17.34

CaSO4(s) U Ca2+(aq) + SO42(aq)

Ksp = [Ca2+][SO42] = 2.4 105
Ksp = x2 = 2.4 105
and x = 4.9 103 M.
let x = [Ca2+] = [SO42]
The molar solubility of CaSO4 is 4.9 103 moles/L.

17.35

CaCO3(s) U Ca2+ + CO32

Ksp = [Ca2+][CO32] = 4.5 109
2+
2
let x = [Ca ] = [CO3 ]
x2 = 4.5 109; x = 6.7 105 M
The solubility of CaCO3 is 6.7 105 M. So, 6.7 105 moles of CaCO3 dissolves in 1 L of H2O. If 100
mL of water are available, 6.7 106 moles of CaCO3 will dissolve. Converting this to #g/100 mL we
multiply by the molar mass of 100 g/mole and determine that 6.7 104 g will dissolve in 100 mL of
water.

17.36

Mg(OH)2 U Mg2+ + 2OH

Ksp = [Mg2+][OH]2 = 7.1 1012

The concentration of OH is determined from the pH:

pOH = 14 12.50 = 1.50
[OH] = 0.032 M
2+
[Mg ] = x
[OH] = 0.032 M
2
Ksp = x(0.032) = 7.1 1012
x = 6.9 109 M
The molar solubility of Mg(OH)2 is 6.9 109 M in a solution with a pH of 12.50.

408

Chapter 17
17.37

Al(OH)3(s) U Al3+ + 3OH

Ksp = [Al3+][OH]3 = 3 1034

The concentration of OH is determined from the pH:

pOH = 14 9.50 = 4.50
[OH] = 3.2 105 M
3+
[OH] = 3.2 105
[Al ] = x
5 3
Ksp = x(3.2 10 ) = 3 1034
x = 9.2 1021
The molar solubility of Al(OH)3 is 9.2 1021 M in a solution with a pH of 9.50.

17.38

Ag2CrO4 (s) U 2Ag+ (aq) + CrO42(aq)

(a)
[Ag+]
[CrO42]
0.200

I
0.200 + 2x
+x
C
0.200 + 2x
+x
E

Ksp = [Ag+]2[CrO42] = 1.2 1012

Ksp = (0.200+2x)2(x)
Assume that x << 0.200
1.2 1012 = (0.200)2(x) x = 3.0 1011
The molar solubility is 3.0 1011 moles/L
(b)
I
C
E

[Ag+]

+2x
+2x

[CrO42]
0.200
0.200 + x
0.200 + x

Ksp = (2x)2(0.200+x)
Assume that x << 0.200
1.2 1012 = (2x)2(0.200) x = 1.2 106
The molar solubility is 1.2 106 moles/L.
17.39

MgOH2 (s) U Mg2+(aq) + 2OH(aq)

(a)
[Mg2+]
[OH]

0.20
I
+x
0.20 + 2x
C
+x
0.20 + 2x
E

Ksp = [Mg2+][OH]2 = 7.1 1012

Assume 2x << 0.20

Ksp = (x)(0.20 + 2x)2
Ksp = (x)(0.20)2 = 7.1 1012
x = 1.8 1010 M
The assumption is valid and the molar solubility of Mg(OH)2 in 0.20 M NaOH is 1.8 1010 moles/L
(b)
I
C
E

[Mg2+]
0.20
0.20 + x
0.20 + x

[OH]

+ 2x
+ 2x

Assume x << 0.20

Ksp = (0.20 + x)(2x)2
Ksp = (0.20)(2x)2 = 7.1 1012
x = 3.0 106 M
The assumption is valid and the molar solubility of Mg(OH)2 in 0.20 M MgSO4 is 3.0 106 moles/L

409

Chapter 17

17.40

Fe(OH)2(s) U Fe2+(aq) + 2 OH(aq)

K sp = Fe 2+ OH

mol OH = 2.20 g NaOH(1 mol/40.01 g NaOH) = 0.0550 mol NaOH

[OH] = mol OH/L solution = 0.0550 mol/0.250 L = 0.22 M

I
C
E

[Fe2+]

+x
x

[OH]
0.22
+ 2x
0.22 + 2x

We assume that x << 0.22, so that 0.22 + 2x 0.22, then we enter the equilibrium values of the above table
into the Ksp expression:
2

K sp = Fe 2+ OH

7.9 1016 = x(0.22)2

x = molar solubility = 1.6 1014 M

Next, we must determine how many moles of Fe(OH)2 are formed in the reaction.
This is a limiting reactant problem.
The number of moles of OH is 0.0550 (see above).
The number of moles of Fe2+ is (0.250 L)(0.10 mol/L) = 0.025 mol
From the balanced equation at the top, we need two OH for every one Fe2+.
This would be 2(0.025 mol) = 0.050 mol OH. Looking at the molar quantities above, we have more than
enough OH so, Fe2+ is our limiting reactant:
0.025 mol Fe(OH)2 will form in 0.25 L solution. If dissolved, this would be a concentration of 0.025
mol/0.25 L = 0.10 M. But from above, the maximum molar solubility of is 1.6 1014 M.
This means that remainder of Fe(OH)2 in excess of this value precipitates:
0.10 1.6 1014 0.10 M.
This works out to 0.25 L(0.10 mol/L) = 0.025 mol Fe(OH)2(89.8 g/mol)
= 2.2 g solid Fe(OH)2 (essentially all of it).
The remaining OH, 0.005 mol, gives a concentration of OH of
0.005 mol OH
= 0.02 M OH
0.250 L
7.9 1016 = [Fe2+][0.02]2
[Fe2+] = 2.0 1012 M
17.41

Ni(OH)2(s) U Ni2+(aq) + 2OH(aq)

mol OH = 1.75 g NaOH(1 mol/40.01 g NaOH) = 0.0437 mol NaOH
First, assume that all of the ions are in solution and no precipitate has formed. At that point the
concentrations are:
0.0437 mol OH
[OH] =
= 0.175 M OH
0.250 L
[Ni2+] = 0.10 M

410

Chapter 17
Next, determine the limiting reactant:
0.10 mol Ni 2+ 2 mol OH

= 0.20 M OH
1 L soln
1 mol Ni 2+

Only 0.175 M OH is available, therefore OH is the limiting reagent.

Using the limiting reagent, assume that all of the OH has precipitated
[OH] = 0.0 M
0.175 mol OH 1 mol Ni 2+
[Ni2+] = 0.10 M Ni2+

2 mol OH
1 L soln

= 0.10 M Ni2+ 0.088 M Ni2+ = 0.012 M Ni2+

From here, calculate the equilibrium concentrations:
I
C
E

[Ni2+]
0.012
+x
0.012 + x

[OH]

+ 2x
2x

We assume that x << 0.012, so that 0.012 + 2x 0.012, then we enter the equilibrium values of the above
table into the Ksp expression:
2

K sp = Ni 2+ OH

6 1016 = 0.012(x)2
x = 2.2 107 M
The amount of Ni(OH)2 formed can be calculated from the amount of OH added to the solution since
essentially all of the OH was precipitated:
1 mol Ni(OH) 2
g Ni(OH)2 = 0.0437 mol OH
2 mol OH

92.71 g Ni(OH)2
= 2.03 g Ni(OH)2

1 mol Ni(OH) 2

To determine the pH of the final solution, the [OH] needs to be found:

From the ICE table, the equilibrium concentration of OH = 2x
2x = 4.4 107 M = [OH]
x = 2.2 107 M
We need to add in the concentration of OH,1 107 M, from the dissociation of water:
[OH] = 4.4 107 M + 1 107 = 5.4 107 M
pOH = log[OH] = log[5.4 107] = 6.27
pH = 14 pOH = 14 6.27 = 7.73
17.42

(a)

CuCl(s) U Cu+(aq) + Cl(aq)

I
C
E

[Cu+]

+x
+x

Ksp = x2 = 1.9 107

(b)

[Cl]

+x
+x

x = molar solubility = 4.4 104 M

CuCl(s) U Cu+(aq) + Cl(aq)

I
C
E

[Cu+]

+x
+x

Ksp = [Cu+][Cl] = 1.9 107

Ksp = [Cu+][Cl] = 1.9 107

[Cl]
0.0200
+x
0.0200 + x

Ksp = (x)(0.0200+x) = 1.9 107 Assume that x << 0.0200

x = molar solubility = 9.5 106 M

411

Chapter 17
(c)

CuCl(s) U Cu+(aq) + Cl(aq)

I
C
E

[Cu+]

+x
+x

Ksp = [Cu+][Cl] = 1.9 107

[Cl]
0.200
+x
0.200 + x

Ksp = (x)(0.200+x) = 1.9 107

Assume that x << 0.200
x = molar solubility = 9.5 107 M
(d)
CuCl(s) U Cu+(aq) + Cl(aq) Ksp = [Cu+][Cl] = 1.9 107
Note that the Cl concentration equals (2)(0.150 M) since two moles of Cl are produced for every mole of
CaCl2.

I
C
E

[Cu+]

+x
+x

[Cl]
0.300
+x
0.300 + x

Ksp = (x)(0.300+x) = 1.9 107

Assume that x << 0.300
x = molar solubility = 6.3 107 M
17.43

AuCl3(s) U Au3+ + 3Cl

(a)

Ksp = [Au3+][Cl]3 = 3.2 1025

let x = [Au3+]; then [Cl] = 3x

Ksp = (x)(3x)3 = 27x4
3.2 1025
= 3.3 107 M
27
The molar solubility of AuCl3 is 3.3 107 M in H2O.

x=

(b)

[Au3+] = x; [Cl] = 0.010 + 3x

Ksp = (x)(0.010 + 3x)3: Assume 3x << 0.010
Ksp = (x)(0.010)3
x = 3.2 1019 M
The molar solubility of AuCl3 is 3.2 1019 M in 0.010 M HCl.

(c)

[Au3+] = x; [Cl] = 0.020 + 3x

Ksp = (x)(0.020 + 3x)3: Assume 3x << 0.020
Ksp = (x)(0.020)3
x = 4.0 1020 M
The molar solubility of AuCl3 is 4.0 1020 M in 0.010 M MgCl2.

(d)

[Au3+] = 0.010 + x; [Cl] = 3x

Ksp = (0.010 + x)(3x)3: Assume x << 0.010
Ksp = (0.010)(3x)3
3.2 1025
= 1.1 108 M
0.27
The molar solubility of AuCl3 is 1.1 108 M in 0.010 M Au(NO3)3.

x=

412

Chapter 17

17.44

Fe(OH)2(s) U Fe2+(aq) + 2 OH(aq)

K sp = Fe 2+ OH = 7.9 1016

pH = 9.50
pOH = 14.00 pH = 4.50
[OH] = 104.50 = 3.16 105 M
[Fe2+]

+x
x

I
C
E

[OH]
3.16 105
+ 2x
(3.16 105) + 2x

Since Ksp for iron(II) hydroxide is so small, we can safely assume that
2x << 3.16 105, so that (3.16 105) + 2x 3.16 105, then we enter the equilibrium values of the
above table into the Ksp expression:
2

K sp = Fe 2+ OH

7.9 1016 = x(3.16 105)2

x = molar solubility = 7.9 107 M

17.45

(a)

Ca(OH)2(s) U Ca2+(aq) + 2OH(aq)

Ksp = [Ca2+][OH]2 = 6.5 105

2+
let 2x = [OH ], [Ca ] = x + 0.10 Ksp = (0.10 + x)(2x)2 = 6.5 105
By successive approximations, x = 0.012
The molar solubility of Ca(OH)2 in 0.10 M CaCl2 is 0.012 moles/L.

(b)

Ksp = [Ca2+][OH]2 = 6.5 105

Ca(OH)2(s) U Ca2+(aq) + 2OH(aq)
let x = [Ca2+], [OH] = 2x + 0.10 Ksp = (x)(2x + 0.10)2 = 6.5 105
By successive approximations, x = 0.0053
The molar solubility of Ca(OH)2 in 0.010 M NaOH is 0.053 moles/L.

17.46

PbCl2(s) U Pb2+ + 2Cl

[Cl] = 0.10 M
[Pb2+][Cl]2 =[Pb2+][0.10]2 = 1.7 105
[Pb2+] = 1.7 103 M

17.47

PbBr2 will be less soluble in a solution of 0.10 M NaBr because the values of Q and Ksp for lead bromide
are dependent upon the [Br]2.

17.48

HC2H3O2 + H2O U H3O+ + C2H3O2

Ka =

Ksp = [Pb2+][Cl]2 = 1.7 105

[H3O+ ][C2 H3O2 ]

= 1.8 105
HC2 H3O 2

First, we calculate the % ionization in water (no added sodium acetate):

I
C
E

[HC2H3O2]
0.10
0.10x
0.10 x

[H3O+]

+x
x

[C2H3O2]

+x
+x

Assume x << 0.10

413

Chapter 17

Ka =

[x][x]
= 1.8 105
[0.10]

x = 1.3 10 3 = [H3O + ]

% ionization = ([H+]/[total acid]) 100 = (1.3 103/0.10) 100 = 1.3 %

Now we calculate the % ionization using 0.050 mol/0.500L = 0.10 M for the concentration of sodium acetate:

I
C
E

[H3O+]

+x
x

[HC2H3O2]
0.10
0.10x
0.10 x

Assume x << 0.10

[x][0.10]
Ka =
= 1.8 105
[0.10]

[C2H3O2]
0.10
+x
0.10 + x

x = 1.8 10-5 = [H3O+ ]

% ionization = ([H+]/[total acid]) 100 = (1.8 105/0.10) 100 = 0.018 %

So the % ionization decreased by (1.3 0.018) = 1.3 %, using correct significant figures. (This does not
mean it has no dissociation, but that the dissociation is very small compared to 1.3%.)
Using the [H+] values above, the pH initially was:
log [H+] = log [1.3 103] = 2.89
After addition of the sodium acetate it was:
log [H+] = log [1.8 105] = 4.74
The pH changes by (4.7 2.9) = +1.85 pH units
17.49

HC2H3O2 + H2O U H3O+ + C2H3O2

Ka =

[H3O+ ][C2 H3O2 ]

= 1.8 105
HC2 H3O 2

First, we calculate the % ionization in water (no added HCl):

I
C
E

[HC2H3O2]
0.10
0.10 x
0.10 x

[H3O+]

+x
x

[C2H3O2]

+x
+x

Assume x << 0.10

Ka =

[x][x]
= 1.8 105
[0.10]

x = 1.3 103 = [H3O+ ]

% ionization = ([H+]/[total acid]) 100 = (1.3 103/0.10) 100 = 1.3 %

Now we calculate the % ionization using 0.025 mol/0.500 L = 0.050 M for the concentration of H3O+:
I
C
E

[HC2H3O2]
0.10
0.10 x
0.10 x

[H3O+]
0.050
+x
0.050 + x

[C2H3O2]

+x
x

Assume x << 0.050

414

Chapter 17

Ka =

[x][0.050]
= 1.8 105
[0.10]

x = 3.6 105 = [C 2 H3O 2 ]

% ionization = ([C2H3O2]/[total acid]) 100 = (3.6 105/0.10) 100 = 0.036 %

So the % ionization decreased by (1.3 0.036) = 1.3%, using correct significant figures. (This does not
mean it has no dissociation, but that the dissociation is very small compared to 1.3%.)
Using the [H+] values above, the pH initially was:
log [H+] = log [1.3 103] = 2.89
After addition of the hydrogen chloride it was:
log [H+] = log [0.050] = 1.30
The pH changes by (1.30 2.89) = 1.59 pH units
17.50

K sp = Ag + Cl = 1.8 1010

K sp = Ag + I = 8.3 1017

AgCl(s) U Ag+ + Cl
AgI(s) U Ag+ + I

When AgNO3 is added to the solution, AgI will precipitate before any AgCl does due to the lower
solubility of AgI. In order to answer the question, i.e., what is the [I] when AgCl first precipitates, we
need to find the minimum concentration of Ag+ that must be added to precipitate AgCl.
Let x = [Ag+]; Ksp = (x)(0.050) = 1.8 1010; x = 3.6 109 M
When the AgCl starts to precipitate, the solution will have a [Ag+] of 3.6 109 M. Now we ask, what is
the [I] if [Ag+] = 3.6 109 M?
So, K sp = Ag + I = (3.6 109)(x) = 8.3 1017; x = 2.3 108 M = [I]

17.51

This problem is similar to Problem 17.50, except that the Ksp constants are closer in value. We first determine
the minimum amount of SO42 that must be added to initiate the precipitation of CaSO4. CaSO4 will precipitate
after SrSO4 due to its larger value for Ksp: Ksp(CaSO4) = 2.4 105 and Ksp(SrSO4) = 3.2 107 (see Table 17.1)
(a)
Let x = Ca 2+ ; K sp = Ca 2+ SO 4 2 = (0.15)(x) = 2.4 105

x = SO 4 = 1.6 104 M

When the SO 4 = 1.6 104 the CaSO4 will start to precipitate. Now we ask, what is the

Sr 2+ if SO 2 = 1.6 104 M?
4

K sp = Sr 2+ SO 42
SrSO4 (s) U Sr2+ (aq) + SO42(aq)

I
C
E

[Sr2+]

+x
+x

[SO42]
1.6 104
1.6 104 + x
1.6 104 + x

K sp = Sr 2+ SO 42 = (x)(1.6 104 + x) = 3.2 107

For this problem, we must solve the quadratic equation and we determine that
x = 4.9 104 M. Thus, the [Sr2+] = 4.9 104 M when the CaSO4 starts to precipitate.

415

Chapter 17
(b)

17.52

Initially the solution had a concentration of 0.15 M. The solution now has a [Sr2+] = 4.9 104.
So, the percentage of Sr2+ precipitated is;
0.15 4.9 10-4
100% = 99.7 %
0.15

In order for a precipitate to form, the value of the reaction quotient, Q, must be greater than the value of
Ksp. For PbCl2, Ksp = 1.7 105 (see Table 17.1).
2

Q = Pb 2+ Cl = (0.0150)(0.0120)2 = 2.16 106. Since Q < Ksp, no precipitate will form.

17.53

In order for a precipitate to form, the value of the reaction quotient, Q, must be greater than the value of
Ksp. For AgC2H3O2, Ksp = 2.3 103.
Q = Ag + C 2 H3O 2 = (0.015)(0.50) = 7.5 103. Since Q > Ksp, a precipitate will form. (Note: The

concentration of C2H3O2 is twice the concentration of Ca(C2H3O2)2 since one mole of Ca(C2H3O2)2
produces two moles of C2H3O2).

17.54

The precipitate that may form is PbBr2(s). To determine if a precipitate will form, a value for the reaction
quotient, Q, must be calculated: Q = [Pb2+][Br]2. In performing this calculation, the dilution of the ions
must be considered:
Q = [0.00500][0.00500]2 = 1.3 107
[Pb2+] = [Br] = 0.00500 M.
If Q > Ksp, a precipitate will form. Ksp for PbBr2(s) is 2.1 106. Therefore, a precipitate will not form.
Hence, the concentrations calculated are the diluted concentrations. Since no precipitate forms, the
concentrations are not equilibrium values.

17.55

Ksp = [Mn2+][OH]2 = 1.6 1013

Ksp = [Cd2+][OH]2 = 5.0 1015
Mn(OH)2 is more soluble, so we need to determine the hydroxide ion concentration when it begins to
precipitate.
x = 1.3 106 M OH
Ksp = [Mn2+][OH]2 = 1.6 1013 = (0.10)(x)2

Use this value for the [OH ] to solve for the concentration of the [Cd2+] left in solution:
Ksp = [Cd2+][OH]2 = 5.0 1015 = (x)[1.3 106]2 x = 3.1 103 M Cd2+

17.56

To solve this problem, determine the value for Q and apply LeChteliers Principle.
(a)

Pb 2+ = (50.0 mL)(0.0100 moles/L)/(100.0 mL) = 5.00 103

Br = (50.0 mL)(0.0100 moles/L)/(100.0 mL) = 5.00 103

Q = Pb 2+ Br = (5.00 103)(5.00 103)2 = 1.25 107

For PbBr2, Ksp = 2.1 106

Since Q < Ksp, no precipitate will form.

(b)

Pb 2+ = (50.0 mL)(0.0100 moles/L)/(100.0 mL) = 5.00 103

Br = (50.0 mL)(0.100 moles/L)/(100.0 mL) = 5.00 102

Q = Pb 2+ Br = (5.00 103)(5.00 102)2 = 1.25 105

For PbBr2, Ksp = 2.1 106

Since Q > Ksp, a precipitate will form.

416

Chapter 17
17.57

In order for a precipitate to form, the value of the reaction quotient, Q, must be greater than the value of
Ksp. For AgC2H3O2, Ksp = 2.3 103.
Ag + = (22.0 mL)(0.100 M)/(67.0 mL) = 3.28 102 M

C H O = (45.0 mL)(0.0260 M)/(67.0 mL) = 1.75 102 M

2 3 2
Q = Ag + C 2 H3O 2 = (3.28 102)(1.75 102) = 5.74 104.

Since Q < Ksp, no precipitate will form.

17.58

Cu(OH)2(s) U Cu2+(aq) + 2 OH(aq)

K sp = Cu 2+ OH

4.8 10-20 = [ 0.10] OH

[OH] = 6.9 1010 M

pOH = log[OH] = log[6.9 1010] = 9.2
pH = 14.00 pOH = 4.8

4.8 is the pH below which all the Cu(OH)2 will be soluble.

Mn(OH)2(s) U Mn2+(aq) + 2 OH(aq)
K sp = Mn 2+ OH

1.6 10-13 = [ 0.10] OH

[OH] = 1.3 106 M

pOH = log[OH] = log[1.3 106] = 5.9
pH = 14.00 pOH = 8.1

8.1 is the pH below which all the Mn(OH)2 will be soluble.

Therefore, from pH = 4.88.1 Mn(OH)2 will be soluble, but some Cu(OH)2 will precipitate out of solution.
17.59

The following reactions are possible:

CaC2O4(s) U Ca2+(aq) + C2O42(aq)
MgC2O4(s) U Mg2+(aq) + C2O42(aq)
+

HC2O4(aq)

H2C2O4(aq) U H (aq) +

Ksp = [Ca2+][C2O42] = 2.3 109

Ksp = [Mg2+][C2O42] = 8.6 105
H + HC2 O 4
= 5.6 102
K a1 =
[ H 2 C2 O 4 ]

HC2O4 (aq) U H (aq) + C2O4 (aq)

H + C2 O 4 2
= 5.4 105
Ka 2 =
HC O
2 4

H2C2O4(aq) U 2H+(aq) + C2O42(aq)

H + C2 O 42
= 3.0 106
KO =
[ H 2 C2 O 4 ]

Assume that the concentration of H2C2O4 at the end of the process is 0.10 M
First, calculate the concentration of C2O42, at which the MgC2O4 will precipitate
Ksp = [Mg2+][C2O42] = 8.6 105
[Mg2+] = 0.10 M
(0.10)(x) = 8.6 105
x = 8.6 104 M = [C2O42]

417

Chapter 17
As long as the concentration of C2O42 is kept below 8.6 104 M, the Mg2+ will remain in solution
In order for the concentration of oxalate to remain below = 8.6 104 M, the pH will be:
2

H + C2 O 42
= 3.0 106
KO =
[ H 2 C2 O 4 ]

H2C2O4(aq) U 2H+(aq) + C2O42(aq)

2

H + 8.6 10 4
= 3.0 106
KO =
[0.10]

[H+] = 0.0188 M
pH = 1.73
By keeping the pH < 1.73, the MgC2O4 will not precipitate.
To precipitate the CaC2O4, a similar calculation needs to be done:
Ksp = [Ca2+][C2O42] = 2.3 109
[Ca2+] = 0.10 M
(0.10)(x) = 2.3 109
x = 2.3 108 M = [C2O42]
As long as the concentration of C2O42 is kept above 2.3 108 M, the Ca2+ will precipitate
In order for the concentration of oxalate to remain above = 2.3 108 M, the pH must be:
2

H + C2 O 42
= 3.0 106
Ka 2 =
[ H 2 C2 O4 ]

H2C2O4(aq) U 2H+(aq) + C2O42(aq)

2

H + 2.3 10 8
= 3.0 106
K=
0.10
[ ]

[H+] = 13.0 M
pH = 1.12
17.60

The less soluble substance is PbS. We need to determine the minimum [H+] at which CoS will precipitate.
Co 2+ [ H 2S]
(0.010)(0.1)

K spa =
=
= 0.5
2
[H + ]2
H+

(from Table 17.2)

(0.010)(0.1)
= 0.045
0.5
pH = log[H+] = 1.35. At a pH lower than 1.35, PbS will precipitate and CoS will not. At larger values of
pH, both PbS and CoS will precipitate.
[H + ] =

17.61

The less soluble substance is SnS so we will determine the maximum amount of H+ that is permitted before
MnS starts to precipitate.
Mn 2+ [ H 2S]
(0.010)(0.1)

K spa =
=
= 3 107 (from Table 17.2)
2
+ 2
+
[H
]
H

[H + ] =

(0.010)(0.1)
7

= 6 106

3 10
pH = log[H+] = 5.2. At pH values equal to or less than 5.2, MnS will not precipitate.

418

Chapter 17

17.62

17.63

(a)

Cu (aq) + 4Cl (aq) U CuCl4 (aq)

K form =

CuCl4 2

Cu 2+ Cl

AgI 2

Ag (aq) + 2I (aq) U AgI2 (aq)

K form =

(c)

Cr3+(aq) + 6NH3(aq) U Cr(NH3)63+(aq)

Cr(NH3 )63+

K form =
3+
Cr NH 6

(a)

(c)

17.65

(b)

(b)

17.64

2+

(a)

Ag (aq) + 2S2O3 (aq) U Ag(S2O3)2 (aq)

2+

2+

Zn (aq) + 4NH3(aq) U Zn(NH3)4 (aq)

4+

Sn (aq) + 3S (aq) U SnS3 (aq)

3+

3+

Ag(S2 O3 )23

Ag + S O 2

2 3

Zn(NH3 )4 2+

K form =
2+
Zn NH 4
3

K form =

Co (aq) + 6NH3(aq) U Co(NH3)6 (aq)

2+

K form =

Ag + I

SnS32

Sn 4+ S2

Co(NH3 )63+

K form =
3+
Co NH 6
3

(b)

Hg (aq) + 4I (aq) U HgI4 (aq)

K form =

(c)

Fe2+(aq) + 6CN(aq) U Fe(CN)64(aq)

K form =

HgI4 2

Hg 2+ I

Fe(CN)64

Fe2+ CN

(a)

Hg (aq) + 4NH3(aq) U Hg(NH3)4 (aq)

Hg(NH3 ) 42+

K form =
Hg 2+ NH 4
3

(b)

Sn4+(aq) + 6F(aq) U SnF62(aq)

K form =

2+

2+

419

SnF6 2

Sn 4+ F

Chapter 17

(c)

17.66

3+

Fe (aq) + 6CN (aq) U Fe(CN)6 (aq)

K form =

Fe(CN)63

Fe3+ CN

There are two events in this net process: one is the formation of a complex ion (an equilibrium which has
an appropriate value for Kform), and the other is the dissolving of Fe(OH)3, which is governed by Ksp for the
solid.
Fe(OH)3(s) U Fe3+(aq) + 3OH(aq)
3+

Fe (aq) + 6CN (aq) U Fe(CN)6 (aq)

K sp = Fe3+ OH = 1.6 1039

K form =

Fe(CN)63

Fe3+ CN

= 1.0 1031

The net process is:

Fe(OH)3(s) + 6CN(aq) U Fe(CN)63(aq) + 3OH(aq)
The equilibrium constant for this process should be:
Fe(CN)63 OH

Kc =
6

CN

The numerical value for the above Kc is equal to the product of Ksp for Fe(OH)3(s) and Kform for Fe(CN)63,
as can be seen by multiplying the mass action expressions for these two equilibria:
Kc = Kform Ksp = 1.6 108
Because Kform is so very large, we can assume that all of the dissolved iron ion is present in solution as the
complex, thus: [Fe(CN)63] = 0.11 mol/1.2 L = 0.092 M. Also the reaction stoichiometry shows that each
iron ion that dissolves gives 3 OH ions in solution, and we have: [OH] = 0.092 3 = 0.28 M. We
substitute these values into the Kc expression and rearrange to get:

[CN ] = 6
=

Fe(CN) 3 OH
6

Kc

(0.092)(0.28)3
1.6 108

Thus we arrive at the concentration of cyanide ion that is required in order to satisfy the mass action
requirements of the equilibrium: [CN] = 7.1 mol L1. Since this concentration of CN must be present in
1.2 L, the number of moles of cyanide that are required is: 7.1 mol L1 1.2 L = 8.5 mol CN.
Additionally, a certain amount of cyanide is needed to form the complex ion. The stoichiometry requires
six times as much cyanide ion as iron ion. This is 0.11 moles 6 = 0.66 mol. This brings the total required
cyanide to (8.5 + 0.66) = 9.2 mol.
9.2 mol 49.0 g/mol = 450 g NaCN are required.

420

Chapter 17
17.67

Ksp = 5.0 1013

AgBr(s) U Ag+ + Br
+
2
3
Kf = 2.0 1013
Ag + 2S2O3 U Ag(S2O3)2

2
3
AgBr(s) + 2S2O3 U Ag(S2O3)2 + Br Kc = Ksp*Kf = 10
2

I
C
E

[S2O3 ]
1.20
2x
1.20 2x

[Br]

+x
+x

[Ag(S2O3)2 ]

+x
+x

Note: Since the AgBr(s) has a constant concentration, it may be neglected.

Kc =
Kc =

[Ag(S2 O3 ) 23 ][Br ]
[S2 O32 ]2

= 10

x2

= 10
(1.20 2x)2
To solve this equation, take the square root of both sides and then solve for x.
x = 0.518 M = [Ag(S2O3)23]
Since 1 mole of AgBr produces 1 mole of Ag(S2O3)23, we can determine the number of grams of AgBr that
will dissolve in 125 mL.
g AgBr = (0.125 L)(0.518 moles/L)(187.77 g/mole) = 12.2 g AgBr

17.68

Kc = Ksp Kform = (1.7 105)(2.5 101) = 4.3 104

17.69

Kc = Ksp Kform = (1.2 1016)(5.3 1018) = 6.4 102

17.70

The applicable equilibria are as follows:

K sp = Ag + I = 8.3 1017

Ag ( CN )
2

Ag+(aq) + 2CN(aq) U Ag(CN)2(aq)

K form =
= 5.3 1018
2
+

Ag CN

The two equations above may be combined and Kc found as follows:

Ag CN ) I
2
(

Kc =
= Ksp Kform = 4.4 102
AgI(s) + 2CN (aq) U Ag(CN)2 (aq) + I (aq)
2

CN

AgI(s) U Ag+(aq) + I(aq)

We begin with 0.010 M CN. This is reduced by some amount (2x) as it reacts with the silver ions, and
[AgI2] is increased by x:
I
C
E

[CN]
0.010
2x
0.010 2x

+x
x

[Ag(CN)2]

+x
x

421

Chapter 17
Now we insert the equilibrium values into the above equation:
Ag CN ) I
2
(
Kc =
= 4.4 102
2

CN

x
x
[ ][ ] = 4.4 102
Kc =
[0.010 2x ]2

Take the square root of both sides and solve for x:

x = 4.9 103
This value represents the change in concentration of I which, from the balanced equation, equals the
change in concentration of AgI(s).
The molar solubility of AgI in 0.010 M KCN is 4.9 103 M.
17.71

In case (a), the formation constant is relatively small indicating that the complex is not very stable. At the
same time, the extremely small value for Ksp indicates that the ML2 solid is very stable. Consequently, the
solution will contain very little M2+.
In case (b), the solubility of ML2 is even smaller than in case (a). However, the large value for the
formation constant indicates that any M2+ ions in solution will react with any ligand present to form the
complex ion. As a result, more of the ML2 solid will dissolve increasing the amount of M2+ in solution.

17.72

Recall that Kinst = 1/ Kform.

Zn(OH)2 (s) U Zn2+(aq) + 2OH(aq)
2+

K sp = Zn 2+ OH = 3.0 10-16

2+

Zn (aq) + 4NH3 (aq) U Zn(NH3)4 (aq) K form

Zn(NH3 ) 42+
=?
=
Zn 2+ NH 4

Combined, this is:

Zn(OH)2 (s) + 4NH3 (aq) U Zn(NH3)42+(aq) + 2OH(aq)
Zn(NH3 )4 2+ OH -

Kc =
4
NH3

[NH3]
1.0
4x
1.0 4x

I
C
E

Kc =

[Zn(NH3)42+]

+x
x

[OH]

+ 2x
2x

[ x ][ 2x ]2
[1.0 - 4x ]4

he problem gives the molar solubility of Zn(OH)2 as 5.7 103 M. This means in one liter of 1.0 M NH3, x
= 5.7 103 moles. Substituting this value in for x, we get Kc = 8.1 107.
Kc = Ksp Kform
8.1 107 = 3.0 1016 Kform
Kform = 2.7 109
Kinst = 1/Kform
Kinst = 1/(2.7 109) = 3.7 1010

422

Chapter 17

17.73

K sp = Cu 2+ OH = 4.8 10-20

Cu(OH)2 (s) U Cu2+(aq) + 2OH(aq)

Cu2+(aq) + 4NH3 (aq) U Cu(NH3)42+(aq)
Combined, this is:

Cu(OH)2 (s) + 4NH3 (aq) U Cu(NH3)42+(aq) + 2OH(aq)

Cu(NH3 )4 2+ OH -

Kc =
4
NH3

I
C
E
Kc =

[NH3]
2.0
4x
2.0 4x

[ x ][ 2x ]2
[ 2.0 4x ]4

= 5.3 107
[Cu(NH3)42+]

+x
x

[OH]

+ 2x
2x

= 5.3 107

Solve for x using successive approximations.

x = 1.1 102
[Cu(NH3)42+] = 1.2 102
Since all of the Cu2+ comes from the Cu(OH)2, the molar solubility of Cu(OH)2 is 1.1 102 M
17.74

The applicable equilibria are as follows:

AgI(s) U Ag+(aq) + I(aq)

K sp = Ag + I = 8.3 10-17

Ag+(aq) + 2I(aq) U AgI2(aq)

K form =

AgI2

= 1 1011

Ag + I

When a solution of AgI2 is diluted, all of the concentrations of the species in Kform above decrease.
However, the decrease of [I] has more effect on equilibrium because its expression is squared. Hence, the
denominator is decreased more than the numerator in the reaction quotient, Q. The system reacts according
to Le Chteliers Principle, by moving to the left (toward reactants) to increase the value of [I].

As the system moves to the left, more Ag+ is created, which has an effect on the first equilibrium above.
Again, Le Chteliers Principle causes the reaction to move to the left to re-establish equilibrium, which
produces AgI(s) precipitate.
The two equations above may be combined and Kc found as follows:
AgI 2
= K K

Kc =
AgI(s) + I (aq) U AgI2 (aq)
sp
form = 8.3 10
I

To answer the second question, we make a table and fill in what we know. We begin with 1.0 M I. This is
reduced by some amount (x) as it reacts with the silver ions, and [AgI2] is increased by the same amount:
I
C
E

[I]
1.0
x
1.0 x

[AgI2]

+x
+x

423

Chapter 17
Now we insert the equilibrium values into the above equation:
AgI 2
= 8.3 106
Kc =

I

[ x ] = 8.3 106
Kc =
[1.0 x ]
x = 8.3 106
This value represents the change in concentration of I which, from the balanced
equation, equals the change in concentration of AgI(s). The given volume is 100 mL, which allows us to
find the amount of AgI reacting:
0.100 L(8.3 106 mol/L) = 8.3 107 mol AgI
8.3 107 mol AgI(234.8 g/mol) = 1.9 104 g AgI
17.75

The applicable equilibria are as follows:

K sp = Ag + I = 8.3 1017

Ag ( I )
2

K form =
= 1 1011
Ag+(aq) + 2I(aq) U AgI2(aq)
2
+

Ag I

The two equations above may be combined and Kc found as follows:
Ag ( I )
2

= Ksp Kform = 8.3 106

AgI(s) + I (aq) U Ag(I)2 (aq) K c =
I

If all of the AgI dissolves, it will be in the form of Ag(I)2, therefore the concentration of Ag(I)2 is:

AgI(s) U Ag+(aq) + I(aq)

0.020 mol Ag ( I )2

= 0.200 M Ag(I)2
0.100 L solution
0.200
[CN] =
=2.4 104 M
8.3 106
The amount of KI that must be added is: (2.4 104 M)(0.100 L) = 2400 mol KI
g KI = (2400 mol KI)(166 g/mol) = 3.98 103 g KI
[Ag(I)2 ] =

Additional Exercises
17.76

We must first calculate the solubility in terms of # mols/L, i.e.,

mol = 7.05 103 g 1 mol Mg(OH) 2 = 1.21 104 M
L
L 58.32 g Mg(OH)
2

Next, use this to establish the individual ion concentrations based on the equilibrium:
Mg(OH)2 U Mg2+ + 2OH

Mg 2+ = 1.21 104 M

OH = 2.42 104 M

Finally, calculate Ksp using the standard expression:

2

K sp = Mg 2+ OH = 1.21 104

)( 2.42 10 )

424

= 7.09 1012

Chapter 17
17.77

To solve this problem, recognize that for a solution having a density of 1.00 g mL1,
1 ppm = 1 mg L1. Therefore, the initial hard water solution has a concentration of 278 mg Ca2+ / 1 L
solution. Converting to molar concentration:
278 mg Ca 2+ 1 g Ca 2+
1 mol Ca 2+
mol Ca 2+
=

L solution 1 L solution 1000 mg Ca 2+ 40.078 g Ca 2+

= 6.94 103 M Ca 2+

The concentration of CO32 is:

2
mol CO32
1.00 g Na 2 CO3 1 mol Na 2 CO3 1 mol CO3

L solution
1 L solution 105.99 g Na 2 CO3 1 mol Na 2 CO3

= 9.43 103 M CO32

Comparing the concentrations of Ca2+ and CO32, we observe that Ca2+ is the limiting reactant. Because of the
small value of Ksp, we can assume that CaCO3 will precipitate using all of the available Ca2+ and leaving
9.43 103 6.94 103 = 2.49 103 M CO32. The question now becomes, how much Ca2+ will be
present in a solution having a [CO32] = 2.49 103 M? Use the solubility product constant for Ksp to
answer this question.
K sp = 4.5 109 = Ca 2+ CO32

9
K sp
4.5 10
Ca 2+ =
=
= 1.8 106 M
3

CO
2.49
10

Converting back to units of ppm (mg L1) we get:

1.8 106 mol Ca 2+
ppm Ca 2+ =

1 L solution

40.08 g Ca 2+

1 mol Ca 2+

1000 mg

1 g

= 7.2 102 ppm Ca 2+

17.78

First, we must calculate the mass of CaSO4 dissolved. The volume is a

cylinder, with V = hr2:
h = 0.50 in (2.54 cm/1 inch) = 1.27 cm
r = 1/2 diameter = 0.50 cm
Therefore:
V = 1.0 cm3, and
mass = 1.0 cm3(0.97 g/cm3) = 0.97 g
However, because it is a hydrate (CaSO42H2O), plaster is only (136.2/172.2 = 0.79) 79% calcium sulfate,
therefore the true mass of CaSO4 is:
Mass = 0.97(.79) = 0.77 g CaSO4
In moles, this is 0.77 g CaSO4 = (1 mol/136.2g) = 0.0056 mol CaSO4
Now we must calculate the volume of water necessary to dissolve 0.77 g of CaSO4. We start by finding its
molar solubility:
K sp = Ca 2+ SO4 2 = 2.4 105

K sp = [ x ][ x ] = 2.4 105

x = 4.9 103 mol/L

425

Chapter 17
So the volume of water needed is:
0.0056 mol(1 L/4.9 103 mol) = 1.2 L
Finally, we find the amount of time needed to produce this much water:
1.2 L (1 day/2.00 L) = 0.60 days, or about 14 hours.
17.79

Initially, both Ag+ and HC2H3O2 are at 1.0 M concentrations. These values will be used to determine if the
AgC2H3O2 will precipitate.
First, determine the concentration of the acetate ion from the equilibrium:
HC2H3O2 U H+ + C2H2O2
H + C2 H3O 2
= 1.8 105
Ka =
HC2 H3O 2

[H3O+]

+x
x

[HC2H3O2]
1.0
x
1.0 x

I
C
E
Assume x << 1.0
[x][x]
Ka =
= 1.8 105
[1.0]

[C2H3O2]

+x
x

x = 4.2 10-3 = [C2 H3O 2 ]

Next, using the concentration of the acetate ion, determine whether or not a precipitate will form.
AgC2H3O2(s) U Ag+ + C2H3O2
Ksp = [Ag+][C2H3O2]
Q = [Ag+][C2H3O2] before equilibrium is established
Q = (1.0 M)(4.2 103 M) = 4.2 103
Q > Ksp therefore a precipitate will form.
17.80

Step 1: Determine the [OH] from the NH3 reaction with water:
NH4+ + OH U NH3 + H2O
NH + OH
4

Kb =
NH3
1.8 10

NH + OH
4

=
NH3

I
C
E
Assume x << 0.10
[ x ][ x ]
1.8 105 =
[0.10]

[NH3]
0.10
x
0.10 x

[OH]

+x
x

[NH4+]

+x
x

x = 1.3 103 = [OH]

Step 2: Find the concentration of Mg2+ at the given concentration of OH.
The concentration of OH from the NH3 is 1.3 103, there is an additional amount of OH from
the equilibrium of the Mg(OH)2, which makes the calculation:
Ksp = 7.1 1012 = [Mg2+][OH]2
7.1 1012 = (x)(1.3 103 + 2x)2
426

Chapter 17
The additional amount of OH can be ignored since it will be less than 1.3 103:
Using the molar solubility of Mg(OH)2 in distilled water:
7.1 1012 = [Mg2+][OH]2
s = [Mg2+] and 2s = [OH]
4s3 = 7.1 1012
s = 1.2 104
The solubility of Mg(OH)2 in distilled water is less than the amount of OH supplied by
the ammonia so we a re justified in ignoring its contribution. We may now solve for x
x = 4.2 106 M = [Mg2+]
The molar solubility of Mg(OH)2 = 4.2 106 M
17.81

(a)

(b)

Mg(OH)2(s) U Mg2+ + 2OH

NH4+ + OH U NH3 + H2O
Mg(OH)2(s) + 2NH4+(aq) U Mg2+(aq) + 2H2O + 2NH3(aq)
We want all of the Mg(OH)2 to go into solution. The NH4+ reacts with any OH produced in the
dissociation of Mg(OH)2 thereby shifting the equilibrium to the right. Using the Ksp value for
Mg(OH)2, we may find the hydroxide ion concentration under these conditions:
Mg(OH)2(s) U Mg2+ + 2OH
2
K sp = Mg 2+ OH

7.1 1012 = [ 0.10] OH

OH = 8.4 106

Now we can use this value in the following, simultaneous equilibrium:

NH4+(aq) + OH(aq) U H2O + NH3 (aq)
Kc = 1/KbNH3 = 1/1.8 105 = 5.6 104
NH3
[0.20]
Kc =
=
= 5.6 104

+
OH NH
8.4 10-6 NH +
4
4

(We know that [NH3] = 0.20 M because in the equation below 2 moles of ammonia are formed for
every one mole of magnesium ion:
Mg(OH)2(s) + 2NH4+(aq) U Mg2+(aq) + 2H2O + 2NH3 (aq))
Solving for [NH4+], we get 0.43 M.
So the total [NH3] + [NH4+] = 0.20 + 0.43 = 0.63 M
One must therefore add 0.63 mol NH4Cl to a liter of solution.
(c)
17.82

The resulting solution will contain 0.20 mol of NH3. Solve the weak base equilibrium problem for
NH3. The pH = 11.28.

Start by determining the [Cl] if the [Pb2+] = 0.0050 M.

Cl =

K sp

1.7 105
= 5.8 102
0.0050

Pb 2+

Then determine the concentration of chloride in a saturated solution, Ksp = 4x3 where x = [Pb2+] and [Cl] =
K sp
2x, x = 3
= 1.6 102 M, Cl = 3.2 102 M

427

Chapter 17
The volume of 0.10 M HCl which needs to be added is:
M1V1 = M2V2
(x mL)(0.10 M HCl) = (3.2 102 M HCl)(x + 100 mL)
0.1 x = 3.2 102x + 3.2
6.8 102 x = 3.2
x = 47 mL
47 mL of 0.10 M HCl need to be added.
17.83

In this problem, we have two simultaneous equilibria occurring:

2

K sp = Mn 2+ OH = 1.6 1013

1
= 1/(7.9 1016) = 1.3 1015
Fe2+(aq) + 2OH(aq) U Fe(OH)2(s)
Kc =
2
+
2
Fe OH

The second equilibrium represents the opposite equation from that of Ksp. Therefore, its value is 1/Ksp for
Fe(OH)2.

Mn(OH)2(s) U Mn2+(aq) + 2OH(aq)

Combined, and omitting spectator ions, this is:

Mn(OH)2(s) + Fe2+(aq) U Mn2+(aq) + Fe(OH)2(s)
Mn 2+
=K
13
Kc =
1.3 1015 = 208
sp (Mn) K c (Fe) = 1.6 10
2
+
Fe

)(

[Fe2+]
0.100
x
0.100 x

I
C
E

[Mn2+]

+x
x

Mn 2+

Kc =
Fe2+

[x]
208 =
[0.100-x ]

20.8 208x = x
20.8 = 209x
x = 0.0995
Therefore, [Fe2+] = 0.100 x = 0.001 M and [Mn2+] = 0.0995 M
Since Ksp for Fe(OH)2 and Mn(OH)2 are so small, we assume there is almost no free hydroxide ion present
and therefore the pH would remain neutral, around 7.
17.84

The reaction for this problem is the formation of Ag(NH3)2+:

Ag(NH3 ) 2+
= 1.6 107
+
2+
Ag (aq) + 2NH3(aq) J Ag(NH3)
K form =
2
+
Ag NH
3

We can rearrange this equation and substitute the values from the text to determine the [Ag+]:
Ag(NH3 ) 2+
2.8 103
=
Ag + =
= 1.8 1010 M
2
2

7
1.6 10 ( 1)
K form NH3

428

Chapter 17

17.85

2+

FeS(s) + 2H (aq) U Fe (aq) + H2S(aq)

I
C
E

K spa

[H+]
8
8 2x
8 2x

[Fe2+]

+x
+x

Fe2+ [ H S]
2 = (x)(x) = 600
=
2
(8 2x)2
H+

K spa

Fe2+ [ H 2S]

=
2
H+

[H2S]

+x
+x

(from Table 17.2)

x
= 24.5
(8 2x)
Solving gives x = 3.92 M. FeS is very soluble in 8 M acid.
take the square root of both sides to get;

17.86

[Ag+] = 0.200 M
[H+] = 0.10 M
First, the concentration of acetate ion needs to be determined at the point that the silver acetate precipitates:
AgC2H3O2(s) U Ag+ + C2H3O2
Ksp = [Ag+][C2H3O2] = 2.3 103
Let x = [C2H3O2]
2.3 103 = (0.200)(x)
x = 1.2 102 M = [C2H3O2]
When NaC2H3O2 is added to the solution, the C2H3O2 will react with the H+ from the nitric acid to form
HC2H3O2. This will give a concentration of 0.10 M HC2H3O2. This will then come to equilibrium
Now, find the concentration of HC2H3O2 using the Ka for acetic acid:
HC2H3O2 U H+ + C2H3O2
[HC2H3O2](0.200 L) + [C2H3O2](0.200 L) = mole NaC2H3O2 that needs to be added.
[HC2H3O2] + [H+] = 0.10 M which is from the nitric acid
[HC2H3O2] = 0.10 M [H+]
H + C2 H3O 2

Ka =
HC2 H3O2
Let x = [H+]
[ x ] 1.2 10 2
-5
1.8 10 =
[0.10 x ]
x = 1.5 104 M = [H+]
[HC2H3O2] = 0.10 M [H+] = 0.10 1.5 104 M = 9.99 104 M
The amount of NaC2H3O2 to be added is:
[HC2H3O2](0.200 L) + [C2H3O2](0.200 L) = mole NaC2H3O2
[9.99 104 M](0.200 L) + [1.2 102 M](0.200 L) = 2.6 103 mole NaC2H3O2
The number of grams to be added is
82.03 g NaC2 H3O2
g NaC2H3O2 = 2.6 103 mole NaC2H3O2
= 0.21 g NaC2H3O2
1 mol NaC2 H3O2

429

Chapter 17
17.87

(a)

The number of moles of the two reactants are:

0.12 M Ag+ 0.050 L = 6.0 103 moles Ag+
0.048 M Cl 0.050 L = 2.4 103 moles Cl
The precipitation of AgCl proceeds according to the following stoichiometry:
Ag+ + Cl J AgCl(s). If we assume that the product is completely insoluble, then 2.4 103
moles of AgCl will be formed because Cl is the limiting reagent (see above.)

143.3 g AgCl
g AgCl = 2.4 103 mol AgCl
= 0.35 g AgCl
1 mol AgCl

(b)

The silver ion concentration may be determined by calculating the amount of excess silver added
to the solution:
[Ag+] = (6.0 103 moles 2.4 103 moles)/0.100 L = 3.6 102 M
The concentrations of nitrate and sodium ions are easily calculated since they are spectators in this
reaction:
[NO3] = (0.12 M)(50.0 mL)/(100.0 mL) = 6.0 102 M
[Na+] = (0.048 M)(50.0 mL)/(100.0 mL) = 2.4 102 M
In order to determine the chloride ion concentration, we need to solve the equilibrium expression.
Specifically, we need to ask what is the chloride ion concentration in a saturated solution of AgCl
that has a [Ag+] = 3.6 102 M.
AgCl(s) U Ag+ + Cl

I
C
E

[Ag+]
0.036
+x
0.036 + x

Ksp = 1.8 1010

[Cl]

+x
+x

K sp = Ag + Cl = (0.036+x)(x) = 1.8 1010

x = 5.0 109 M if we assume that x<<0.036

Therefore, [Cl] = 5.0 109 M.

(c)

The percentage of the silver that has precipitated is:

(2.4 103 moles)/(6.0 103 moles) 100% = 40%

17.88

Let x = mols of PbI2 that dissolve per liter;

Let y = mols of PbBr2 that dissolve per liter.
Then, at equilibrium, we have
[Pb2+] = x + y, [I] = 2x and [Br] = 2y
We know:
PbBr2(s) U Pb2+ + 2Br
PbI2(s) U Pb2+ + 2I

Ksp = 2.1 106 = [Pb2+][Br]2

Ksp = 7.9 109 = [Pb2+][I]2

430

Chapter 17
Substituting we get: 2.1 106 = (x + y)(2y)2 and 7.9 109 = (x + y)(2x)2
Solving for x and y we find:
x = 4.85 104
y = 7.91 103
Thus, [Pb2+] = 8.40 103 M, [I] = 9.70 104 M and [Br] = 1.58 102 M
Note: [Br] > [I] because PbBr2 is more soluble than PbI2.
17.89

A saturated solution of La2(CO3)3 satisfies the following equilibrium expression:

2

K sp = 4.0 1034 = La 3+ CO32

If [La3+] = 0.010 M, then the carbonate concentration of a saturated solution is:

CO 2 =
3

K sp
3

4.0 1034

= 1.6 1010

La
( 0.010 )

We do the same calculation for PbCO3:

K sp = 7.4 1014 = Pb 2+ CO32

If [Pb2+] = 0.010 M, then the carbonate concentration of a saturated solution is:

K sp
7.4 1014
CO32 =
=
= 7.4 1012 M

0.010
Pb 2+

Therefore, at a carbonate ion concentration between 7.4 1012 M and 1.6 1010 M, PbCO3 will
precipitate, but La2(CO3)3 will not precipitate. The upper limit for the carbonate ion concentration is
therefore 1.6 1010 M.
3+

The equilibrium we need to look at now is: H2CO3(aq) U 2H+(aq) + CO32(aq)

The Ka for this reaction is the product of Ka1 and Ka2 for carbonic acid. From Table 18.1 we see that Ka1 =
4.5 107 and Ka2 = 4.7 1011. So the equilibrium expression and value for the reaction of interest is:
2

H + CO32
= K K = 2.1 1017
Ka =
a1
a2
H 2 CO3

This equation is rearranged and the values above and the values given in the problem are substituted in
order to determine the pH range over which PbCO3 will selectively precipitate:
+

H =

K a H 2 CO3
=
CO 2
3

( 2.1 10 )(3.3 10 )
17

CO 2
3

If we substitute CO32 = 7.4 1012 M we determine H + = 3.1 104 M and the pH = 3.51.

Substituting CO32 = 1.6 1010 M , H + = 6.6 105 M and

pH = 4.18.
Consequently, if [H+] = 6.6 105 M (pH = 4.18), La2(CO3)3 will not precipitate but PbCO3 will precipitate.
At pH = 3.51 and below, neither carbonate will precipitate.

431

Chapter 17
17.90

Three reactions are occurring in the solution:

1)

Cu2+(aq) + 4NH3(aq) U Cu(NH3)42+(aq)

Cu(NH3 ) 4
Kform = 1.1 1013 =
Cu 2+ NH 4

2)

NH3(aq) + H2O U NH4+(aq) + OH(aq)

NH 4+ OH

Kb = 1.8 105 =
NH3
2

Ksp = 4.8 1020 = Cu 2+ OH

Starting with the first reaction, using the Kform of Cu(NH3)42+, calculate the concentration of NH3.
The concentration of Cu2+ before any reaction has occurred is 0.050 M, and the concentration of NH3
before any reaction has occurred is 0.50 M. Assume that all of the Cu2+ has reacted and then the reaction
has come to equilibrium. Therefore, the initial concentration of Cu2+ is 0 and the initial concentration of
NH3 is 0.50 M (4 0.05 M)
3)

I
C
E

Cu(OH)2(s) U Cu2+ + 2OH

[Cu2+]

+x
+ 2x

[NH3]
0.30
+ 4x
0.30 + 4x

Cu(NH3)42+
0.050 M
x
0.050 x

Cu(NH3 ) 4
Kform = 1.1 1013 =
Cu 2+ NH 4

3
[0.050 x ]
Kform = 1.1 1013 =
[ 2x ][0.30 + 4x ]4

assume x << 0.050

x = 2.8 1013
[NH3] = 0.30
[Cu2+] = 5.6 1013
Next, determine the [OH] from the reaction of NH3 with H2O
NH3(aq) + H2O U NH4+(aq) + OH(aq)

I
C
E

[NH4+]

+x
x

[NH3]
0.30
x
0.30 x

NH 4+ OH

Kb = 1.8 105 =
NH3

OH

+x
x

NH 4+ OH

Kb = 1.8 10 =
NH3
5

Kb = 1.8 105 =

[ x ][ x ]

assume x << 0.30

[0.30 x ]

x = 2.3 103 = [OH]

Finally, with the concentration of OH and the concentration of Cu2+, determine if any precipitate has
formed:
Ksp = 4.8 1020 = Cu 2+ OH

[Cu2+] = 5.6 1013

Cu(OH)2 U Cu2+ + 2OH

[OH] = 2.3 103

432

Chapter 17

Q = Cu 2+ OH = (5.6 1013)(2.3 103)2 = 3.0 1018

Q > Ksp therefore a precipitate forms. Assume that all of the Cu2+ has reacted with the OH and
then the solution returns to equilibrium

I
C
E

[Cu2+]

+x
+x

[OH]
2.3 103
+ 2x
2.3 103 + 2x

Ksp = 4.8 1020 = Cu 2+ OH

Ksp = 4.8 1020 = [ x ] 2.3 10 3 + 2x

x = 9.1 1015 M = [Cu2+]

17.91

In order to answer this question, we need the [OH] at equilibrium. Mg(OH)2 is a sparingly soluble
compound. According to Table 17.1, Ksp = 7.1 1012.
MgOH2(s) U Mg2+(aq) + 2OH(aq)

I
C
E

[Mg2+]

+x
+x

K sp = Mg 2+ OH

[OH]

+ 2x
+ 2x

Ksp = (x)(2x)2 = 4x3 = 7.1 1012

x = 1.2 104 M, [OH] = 2x = 2.4 104 M:
The pH = 14.00 pOH = 10.38.
17.92

x << 2.3 103

pOH = log[OH] = 3.62

Al(OH)3 has such an exceedingly small Ksp, there is almost no dissociation in

pure water. Therefore, the pH would be expected to be about 7.
In doing the calculations, this is borne out:
K sp = Al3+ OH

3 1034 =

[ x ][3x ]3

x = 1.8 109
[OH] = 5.5 109
[OH] = (1 107) + (5.5 109) = 1.055 107
pOH = 6.98
pH = 7.02
17.93

Fe(OH)3(s) U Fe3+ + 3OH

I
C
E

[Fe3+]

+x
+x

Ksp = [Fe3+][OH]3 = 1.6 1039

[OH]
1.0 107
+ 3x
1.0 107 + 3x

Assume 3x << 1.0 107, Ksp = (x)(1.0 107)3, solving for x we get, x = 1.6 1018 M. Thus, 1.6 1018
mol of Fe(OH)3 dissolve in 1 L of water.
433

Chapter 17
17.94

At its simplest, this is only a Ksp problem.

The concentration of Mn2+ is (0.400 L)(0.10 M Mn2+)/(0.500 L) = 0.080 M Mn2+
K sp = Mn 2+ OH

1.6 10-13 = [ 0.080] OH

OH = 1.4 10-6

When [OH] = 1.4 106 M, Mn(OH)2 precipitates.

0.100 L(2.0 mol/L) = 0.20 mol NH3 are added to 400 mL solution which would make an initial
concentration of 0.20 mol/0.500 L = 0.40 M NH3. The following equilibrium is set up:
K b = 1.8 10-5

H2O + NH3 U NH4+(aq) + OH(aq)

The problem tells us that all of the Sn2+ is precipitated as Sn(OH)2:

Sn2+(aq) + 2OH(aq) U Sn(OH)2(s)
The concentration of the Sn2+ is (0.400 L)(0.10 M Sn2+)/(0.500 L) = 0.080 M Sn2+, just before it precipitates. The
Sn2+ immediately uses the first 2(0.080 M) = 0.16 M OH which is produced from the reaction of ammonia with
water above, using 0.16 M NH3. This effectively brings our initial concentration of NH3 to 0.24 M.
Now we determine how much NH3 will produce [OH] = 1.3 106 M.
K b = 1.8 10-5

H2O + NH3 U NH4+(aq) + OH(aq)

I
C
E
Kb

[NH3]
x
1.2 106
?

[NH4+]

+ 1.2 106
1.2 106

[OH]
1.0 107
+ 1.2 106
1.3 106

NH 4+ OH

=
NH3

1.8 10

-5

1.2 10-6 1.3 10-6

=
NH3

[NH3] = 8.7 108

Therefore the initial [NH3] should be 8.7 108 + 1.2 106 = 1.3 106. So we want to reduce [NH3] by
0.24 1.3 106 = 0.23999 M, essentially by 0.24 M. This would require adding equimolar amounts of
HCl, or:
0.500 L(0.24 mol NH3/L)(1 mol HCl/1 mol NH3)(36.5 g HCl/1 mol HCl)
= 4.4 g HCl.
(The difficulty here arises from the fact that such a small amount of OH is required to precipitate the Mg2+
from solution that even a minimal amount of NH3 produces enough hydroxide ion to do so.)

434

Chapter 17
17.95

The reaction that will dissolve the Mg(OH)2 is:

Mg(OH)2 + 2H+ J Mg2+ + 2H2O
The concentration of H+ in the solution, before any reaction has occurred between the acid and the Mg(OH)2, is
(0.025 L)(0.10 M HCl) = 2.5 103 mol HCl
2.5 103 mol/1.000 L = 2.5 103 M
Since all of the H+ will react with the solid Mg(OH)2, the amount of Mg2+ in solution will be:
1 mol Mg 2+
2.5 103 mol HCl
= 1.3 103 mol Mg2+
2 mol H +

Find the equilibrium concentration of OH with 1.3 103 M Mg2+

Ksp = [Mg2+][OH]2 = 7.1 1012
7.1 1012 = (1.3 103)(x)2
x = 7.4 105 = [OH]
pOH = log[OH] = log(7.4 105) = 4.13
pH = 14 pOH = 14 4.13 = 9.87

17.96

There are two reactions that have to be considered here: the dissociation of CaCO3 in water,
CaCO3(s) J Ca2+(aq) + CO32(aq)
Ksp = [Ca2+][CO32] = 4.5 109
and the ionization of carbonate ion in water,
CO32(aq) + H2O J HCO3(aq) + OH(aq)

Kb =

[OH ][HCO3 ]
2

[CO3 ]
Assuming that all of the CO32 reacts with the water, the net reaction is:
CaCO3(s) + H2O(l) J Ca2+(aq) + HCO3(aq) + OH(aq)
Kc = Ksp Kb = [Ca2+][HCO3][OH] = 8.1 1013

= 1.8 104

We can obtain [OH] from the pH:

pOH = 14 pH = 14 8.50 = 5.50
[OH] = 10pOH = 105.50 = 3.2 106 M
Assume that [Ca2+] = [HCO3] = x
Kc = 8.1 1013 = (x)(3.2 106 M)(x) = (x)2(3.2 106 M)
Solve for x:
x = 5.0 104 M = [Ca2+] = [HCO3]
2+
The [Ca ] is equal to the molar solubility. Thus, the molar solubility of CaCO3 is 5.0 104 M.
17.97

First, lets examine the question to make clear what is happening. A solution contains 0.20 M Ag+ ions and
0.10 M acetate ions. The ion product of these two (0.020) is less than Ksp for silver acetate (2.3 103), so
the silver acetate remains in solution. There are also H+ ions (H3O+) in the solution as a result of the
following equilibrium (OAc will symbolize acetate):
H2O + HOAc U H3O+(aq) + OAc(aq)
The amount of H3O may be found by using the Ka for acetic acid:
+

[HOAc]
0.10
x
0.10 x

I
C
E

Ka

[H3O+]

+x
X

[OAc]

+x
x

H3O + OAc

=
[ HOAc]

1.8 10-5 =

[ x ][ x ]

[0.10

x]

x 1.3 10
So [H3O+] = 1.3 103 M.
435

Chapter 17
However, when F is added to the solution (in the form of KF), the following equilibrium takes place:
F(aq) + H3O+(aq) U H2O + HF
This depletes H3O+ ions from the solution, which causes the first equilibrium above to move to the right,
producing more acetate ions. When the acetate ion concentration hits some minimum value (determined by
Ksp) silver acetate will precipitate. That value may be found as follows:
K sp = Ag + OAc

2.3 103 = [ 0.20][ x ]

x = 0.012 mol/L
So the problem becomesHow many grams of KF must be added such that the acetate concentration
increases to 0.012 M? This is now a simultaneous equilibrium problem:
K a = 1.8 105

H2O + HOAc U H3O+(aq) + OAc(aq)

F(aq) + H3O+(aq) U H2O + HF K c =

1
1
=
= 1.5 103
K a 6.8 104

(Note the above equation is simply the reverse of that for the Ka of HF, so Kc = 1/Ka.)
Combined, this becomes:
F(aq) + HOAc U HF + OAc(aq)

)(

K c = K a K b = 1.8 105 1.5 103 = 2.7 102

Recall that we have already found the initial concentrations of OAc and HOAc above. Using this information,
and the fact that we want the final [OAc] to be 1.2 102, we can begin to fill out the table below.

I
C
E

[F]
x
0.011
?

[HOAc]
0.099
0.011
0.088
Kc =

[HF]

+ 0.011
0.011

[OAc]
1.3 103
+ 0.011
0.012

[ HF] OAc

F [ HOAc ]

[0.011][0.012]
2.7 102 =
F [ 0.088]

[F] = 0.056 M

Placing this value into the table as the equilibrium concentration of [F], we find the initial [F] must be
0.056 + 0.011 = 0.067 M.
Therefore the amount of KF needed in the 200 mL solution is:
0.200 L(0.067 mol KF/L)(58.01 g KF/1 mol KF) = 0.78 g KF
17.98

(1)
(2)

In order, Figure C J Figure B J Figure E

Figures A and D are excluded because PbBr2 will precipitate before PbCl2.

436

Bringing It Together: Chapters 13 17

1.

The five factors that affect the rates of reactions are:

(a)
Chemical nature of the reactants
(b)
Ability of the reactants to come in contact with each other
(c)
Concentrations of the reactants
(d)
Temperature
(e)
Availability catalysts

2.

rate = (0.60 L mol1 s1)[I][OCl]

(a)
rate = (0.60 L mol1 s1)[0.0100 mol L1][0.0200 mol L1]
= 1.2 104 mol L1 s1
(b)
rate = (0.60 L mol1 s1)[0.100 mol L1][0.0400 mol L1]
= 2.4 103 mol L1 s1

3.

(a)

rate = k[A]n[B]m
First, compare the first and third experiments, in which there has been an increase in concentration
by a factor of 2 for A while the concentration of B is held constant. This has caused an increase in
rate of:
rate of reaction 3 k[0.020]n [0.010]m [0.020]n
=
=
= 2n
rate of reaction 1 k[0.010]n [0.010]m [0.010]n
=
rate = k[A]2[B]m

8.0 104 mol L1 s 1

2.0 10
n=2

mol L

= 4.00 = 22

Second, compare the second and third experiment, in which there has been an increase in
concentration by a factor of 2 for B while the concentration of A is held constant. This has caused
an increase in rate of:
rate of reaction 2 k[0.020]n [0.020]m [0.020]m
=
=
= 2m
rate of reaction 3 k[0.020]n [0.010]m [0.010]m
=
rate = k[A]2[B]0

8.0 104 mol L1 s 1

8.0 104 mol L1 s 1

m=0

= 1.00 = 20

(b)

The rate constant:

8.0 104 mol L1 s1 = k[0.020 mol L1]2[0.010]0
k = 2 L mol1 s1

(c)

rate = 2 L mol1 s1[0.017 mol L1]2[0.033 mol L1]0

rate = 5.8 104 mol L1 s1

4.

The order of the reaction with respect to that reactant is 1

5.

(a)

t1/2 =
t1/2 =

t1/2 =

ln 2
k

ln 2
2.41 10
ln 2

2.22 10

= 2.88 105 s
= 3.12 105 s

437

Bringing It Together: Chapters 13 17

(b)

[C2(NO2)6] = 0.100 M
[ A]0
ln
= kt
[ A]t
ln

(c)

(d)

[0.100] = 2.41106 s1 500 min 60 s

)
1 min
[x] (

x = 9.30 102 mol L1

k
1
E a
1
ln 2 =

1
1
k1 8.314 J mol K T2 T1
2.22 104 s 1
E a
1
1
=

ln
2.41 106 s 1 8.314 J mol 1 K 1 373 K 343 K

1
37.6 J mol = Ea (2.34 104)
Ea = 1.60 105 J mol1
k
1
E a
1
ln 2 =

1
1
k1 8.314 J mol K T2 T1
2.22 104 s 1 1.60 105 J mol 1 1
1

ln
=
1
1
1 373 K

393 K
xs

8.314 J mol K
x s1 = 3.07 103 s1

6.

(a)

(b)

1 1 1 1
=
2 2 2 8
ln 2
=k
t1

An eight of the 90 Sr will be left.

ln 2
= 0.025 y1
28 y

k=

[ A ]0
= kt
[ A ]t
[ A ]0
ln
= 0.025 y 1 ) (168 y)
[ A ]t (
[ A ]0
1
=
[ A ]t 0.015
[ A ]0
ln
= kt
[ A ]t
ln

(c)

ln

(d)

1
1
16

t = 111 y
[ A ]0
ln
= kt
[ A ]t
ln

1
1
6

= 0.025 y 1 t

= 0.025 y 1 t

t = 71.7 y
438

Bringing It Together: Chapters 13 17

7.

(a)

t1/2 =
t1/2 =

(b)

1
k (initial concentration of reactant)
1
1.0 10 4 L mol 1 s 1 (0.250 M)

= 4 104 s

1
1

= kt
[ A ]t [ A ]0
1
60 s
= 1.0 10 4 s 1 ( 30 min )

0.250 mol L1
1 min

[A]30 min = 0.239 mol L1

[B]30 min = 0.150 M (0.250 M 0.239 M) = 0.139 M
1

[ A ]t

8.

Reaction mechanism is an entire series of elementary processes to describe the steps involved in a reaction.
Rate-determining step is the slowest step in a reaction mechanism
Elementary process is a reaction whose rate law can be written from its own chemical equation, using its
coefficients as exponents for the concentration terms.

9.

rate = k[O3]

10.

The activation energy for the forward reaction is the difference in energy between the reactants and the
transition state. The activation energy for the reverse reaction is the difference in energy between the
products and the transition state. The heat of reaction is H.
11.

A heterogeneous catalyst increases the rate of a chemical reaction by providing another reaction pathway
with a lower activation energy.

12.

(a)
(b)

(c)

The initiation step is

C2H6 J 2CH3
The propagation steps are
CH3 + C2H6 J CH4 + C2H5
C2H5 J C2H4 + H
H + C2H6 J C2H5 + H2
The termination step is
H + C2H5 J C2H6

439

Bringing It Together: Chapters 13 17

13.

(a)
(b)
(c)

14.

[ NO]3
[ NO2 ][ N 2 O]
[SO2 ]
Ni 2+ CO32

The equilibrium constant is very small, therefore the reaction does not proceed appreciably to products.
[HF] = 0.010 M
[HF]
[H2]
[F2]
0.010

I
2x
+x
+x
C
0.0102x
+x
+x
E
Kc =

[ H 2 ][ F2 ]
[ HF]2

x << 0.010
1 1013 =

[ x ][ x ]
[0.010 2x ]

= 1 1013

[ x ][ x ]
[0.010]2

Take the square root of both sides and solve for x

x = 3.2 109
[H2] = [F2] = 3.2 109
15.

K p = K c (RT)

n g

2NO2(g) U N2O4(g)
ng = 1
6.5 102 = Kc[(0.0821 L atm mol1 K1)(393 K)]1
Solve for Kc
Kc = 2.1
16.

NO2(g) + SO2(g) U NO(g) + SO3(g)

I
C
E
K c = 3.60 =

Kc = 3.60 =

[NO2]
0.0200
x
0.0200x

[SO2]
0.0200
x
0.0200x

[ NO]SO3
[ NO2 ][SO2 ]
[ x ][ x ]
[0.0200 x ][0.0200 x ]

Take the square root of both sides

x
1.90 =
0.0200 x
Solve for x.
x = 0.0131
[NO2] = [SO2] = 6.90 103 M
[NO] = [SO3] = 0.0131 M

440

[NO]

+x
+x

[SO3]

+x
+x

Bringing It Together: Chapters 13 17

I
C
E
K c = 3.60 =

Kc = 3.60 =

[NO2]
6.90 103 M
+x
6.90 103 +x

[SO2]
6.90 103 M
+x
6.90 103 +x

[NO]
0.0151
x
0.0151x

[SO3]
0.0151
x
0.0151x

[ NO]SO3
[ NO2 ][SO2 ]
[0.0151 x ][0.0151 x ]
[0.00690 + x ][0.00690 + x ]

Again take the square root of both sides and solve for x.
0.0151 x
1.90 =
0.00690 + x
x = 6.86 104
[NO2] = [SO2] = 7.59 103 M
[NO] = [SO3] = 1.44 102 M
17.

(a)
(b)
(c)
(d)
(e)

Increase
Increase
Decrease
Decrease
No change

18.

Kw = [H+][OH] = 9.5 1014

[H+] = [OH] = 3.1 107
pH = 6.51
The solution is neither acidic nor basic because the concentration of the hydronium ion equals the
concentration of the hydroxide ion.

19.

The concentration of OH is 4.7 107 g L1

The molar concentration of OH is:
4.7 107 g OH 1 mol OH
= 2.76 108 M
[OH] =
1 L solution 17.01 g OH

pOH = log[OH] = log(2.76 108 M) = 7.56

pH = 14 pOH = 14 7.56 = 6.44
The water is acidic.

20.

H3AsO4 is a stronger acid since there are more oxygens on the As. The electrons are more electronegative
and pull electron density away from the OH bonds.

21.

H2Te

22.

(a)
(b)

H2SO3
N2H5+

23.

(a)
(b)
(c)

SO32
N2H3
C5H5N

24.

CH3NH2 and CH3NH3+

NH4+ and NH3

441

Bringing It Together: Chapters 13 17

25.

An amphoteric substance can behave as either an acid or a base.

A Lewis acid is an electron pair acceptor.
A Lewis base is an electron pair donor.

26.
O

O
O

S
O

27.

The stronger binary acid than Y would be Z. Binary acid strength increase left to right across a period.

28.

(a)
(b)
(c)

(d)

C6H5OH(aq) + H2O(l) C6H5O(aq) + H3O+(aq)

C6 H 5 O H 3 O +

Ka =
C6 H5 OH
[C6H5OH] = 0.550 M since the amount of dissociation is negligible
[H3O+] = log(pH) = log(5.07) = 8.51 106 M
[C6H5O] = 8.51 106 M since all of the H3O+ comes from the dissociation of the phenol
C6 H 5 O H 3 O +
8.51 106 8.51 106

= 1.32 1010
Ka =
=
C6 H5 OH
[0.550]
pKa = log Ka = log(1.32 1010) = 9.88
1 1014
1 1014
= 7.58 105
=
Kb =
10
Ka
1.32 10
pKb = log Kb = log(7.58 105) = 4.12

29.

(a)
(b)

pKb = 14 pKa = 14 11.68 = 2.32

C7H3SO3 + H2O U C7H3SO3H + OH
The solution will be basic
C7 H3SO3 H OH
Kb =
= 4.79 103
C7 H3SO3

I
C
E

4.79 103 =

[C7H3SO3]
0.010
x
0.010x

[C7H3SO3H]

+x
+x

[OH]

+x
+x

[ x ][ x ]

[0.010 x ]

x will be large compared to 0.010 M. Therefore we need to solve it either by successive

approximations or the quadratic equation.
x = 4.92 103 = [OH]
pOH = 2.31
pH = 11.69

442

Bringing It Together: Chapters 13 17

30.

Let Cod stand for codeine

Cod + H2O U CodH+ + OH
CodH + OH

= 1.6 106
Kb =
Cod
[ ]

I
C
E

1.6 106 =

[Cod]
0.0115
x
0.0115x

[CodH+]

+x
x

[OH]

+x
x

[ x ][ x ]

[0.0115 x ]

x is large compared ot 0.0115, therefore solve for x using either the quadratic equation or successive approximations
x = 1.3 104 = [OH]
pOH = 5.79
pH = 14 pH = 8.21
31.

CH3NH2(aq) + H2O U CH3NH3+(aq) + OH(aq)

CH3 NH3+ OH

Kb =
CH3 NH 2

32.

pKb = 3.43
pKa of its conjugate acid = 14 pKb = 14 3.43 = 10.57

33.

(a)

(b)

1 mol H 2 C6 H 6 O6
176.1 g H C H O = 0.142 M H2C6H6O6

2 6 6 6
HC6 H 6 O6 H 3O +

= 7.94 105
Ka1 =
H2C6H6O6 U HC6H6O6 + H3O+
H 2 C6 H 6 O6
C6 H 6 O 6 2 H 3 O +

= 1.62 1012
HC6H6O6 U C6H6O62 + H3O+
Ka2 =

HC6 H 6 O6

+
Since all of the H3O will come from the first equilibrium reaction, it can be calculated as follows:
3.12 g H 2 C6 H 6 O6
M ascorbic acid solution =
0.125 L

I
C
E

[H2C6H6O6]
0.142
x
0.142x

[HC6H6O6]

+x
x

[H3O+]

+x
x

HC6 H 6 O6 H3O +

7.94 10 =
H
C
H
O
2 6 6 6
5

7.94 105 =

[ x ][ x ]

[0.142 x ]

Solve for x
x = 3.32 103 = [H3O+]
pH = log[H3O+] = log(3.32 103) = 2.48
[C6H6O62] = 1.62 1012
[HC6H6O6] = [H3O+] in the Ka2 equation, these cancel

443

Bringing It Together: Chapters 13 17

34.

pH = pKa + log

A
initial
[ HA ]initial

A
initial
4.50 = 4.74 + log
[ HA ]initial
A
initial
0.24 = log
[ HA ]initial

10

0.24

A
initial
=
[ HA ]initial

A
initial
= 0.575
[ HA ]initial

35.

36.

(a)
(b)

C2H3O2 + H+ J HC2H3O2
HC2H3O2 + OH J C2H3O2 + H2O

C2 H 3 O 2 H3O +

Ka = 1.8 10 =
HC
H
O
2 3 2
5

[0.10] H3O+
[0.15]

= 1.8 105

[H3O+] = 2.7 105

pH = 4.57
[HC2H3O2]final = (0.15 0.04)M = 0.11 M
[C2H3O2]final = (0.10 + 0.04)M = 0.14 M

[0.14] H3O+
= 1.8 105
0.11
[ ]
[H3O+] = 1.4 105
pH = 4.85
The change in pH is 0.28 pH units.
37.

(a)
(b)

Propanoic acid, pKa = 4.87 and its salt, sodium propionate

This problem is best solved using two equations and two unknowns:
mol A
pH = pKa + log
mol HA
A + 0.005
5.10 = 4.87 + log
[ HA ] 0.005
A
5.00 = 4.87 + log
[ HA ]

444

Bringing It Together: Chapters 13 17

A + 0.005
0.23 = log
[ HA ] 0.005
A
0.13 = log
[ HA ]

10

0.23

A + 0.005
=
[ HA ] 0.005

10

0.13

A
=
[ HA ]

[A] = 100.13[HA]
100.23 =

100.13 [ HA ] + 0.005

[ HA ] 0.005

0.23

10 ([HA] 0.005) = 100.13[HA] + 0.005

1.698[HA] 0.008491 = 1.349[HA] + 0.005
0.3493[HA] = 0.01349
[HA] = 0.03865 M
[A] = 100.13(0.03865 M) = 0.05214 M

(c)

For 625 mL (0.625 L) of solution:

For determining the mass of propionic acid needed:
0.03865 mol C3 H 6 O 2 74.09 g C3 H 6 O2
g C3H6O2 = 0.625 L
= 1.79 g C3H6O2

1L

1 mol C3 H 6 O2
For determining the mass of sodium propionate:
0.05214 mol NaC3 H5 O2 96.07 g NaC3 H5 O 2
g NaC3H5O2 = 0.625 L
= 3.13 g

1L

1 mol NaC3 H5 O 2
NaC3H5O2
From the above calculation:
The concentration of propionic acid is 0.03865 M.
The concentration of sodium propionate is 0.05214 M.

38.

(a)
(b)
(c)
(d)

Neutral
Acidic
Acidic
Acidic

39.

pKb = 14 pKa = 14 4.87 = 9.13

[ HA ] OH
Kb =
= 7.41 1010

A

All of the acid has been converted into the salt at the equivalence point.
(0.115 M)(50.00 mL) = (0.100 M)(x mL)
x = 57.50 mL
total volume is 107.50 mL
[A] = 0.05349 M
[HA] = [OH] = x

445

Bringing It Together: Chapters 13 17

7.41 1010 =

( x )( x )

[0.05349]

x = 6.296 106 M = [OH]

pOH = 5.201
pH = 8.799
Thymol blue or phenolphthalein would be good indicators.
40.

Kb1 =

K w 1.0 1014
=
= 6.3 103
K a 2 1.6 1012

I
C
E

[C6H6O62]
0.050
x
0.050x

[HC6H6O6]

+x
x

[OH]

+x
x

HC6 H 6 O6 OH

= [ x ][ x ] = 6.3 103
C6 H 6 O6 2
[0.050 x ]

x is too large to make a simplifying assumption, therefore solve for x either using the quadratic equation or
by successive approximations.
x = 0.015 = [OH]
pOH = 1.82
pH = 12.18

41.

Since half of the acid is neutralized the concentration of the acid is equal to the concentration of its
conjugate base, the pKa can be determined:
A
pH = pKa + log
[ HA ]
3.56 = pKa + log 1
pKa = pH = 3.56
Ka = 10pKa = 103.56 = 2.75 104

42.

A
pH = pKa + log
[ HA ]

pKa = 14 pKb
pKa = 14 4.74 = 9.26
A
9.26 = 9.26 + log
[ HA ]

pKb = log Kb = log 1.8 105

[A] = [HA]
[NH4+] = 0.100 before the addition of NaOH. In order for the two concentrations to be equal, half as much
NaOH must be added:
(0.100 L NH4+)(0.100 M NH4+ solution) = 0.0100 mol NH4+
(0.0100 mol NH4+)(0.5) = 0.00500 mol NaOH
40.00 g NaOH
0.00500 mol NaOH
= 0.200 g NaOH
1 mol NaOH

446

Bringing It Together: Chapters 13 17

43.

Ksp = [Ag+]2[CrO42]
[Ag+] = 2 (6.7 105 M) = 1.34 104 M
[CrO42] = 6.7 105 M
Ksp = (1.34 104)2(6.7 105)
Ksp = 1.2 1012

44.

Mg(OH)2(s) U Mg2+(aq) + OH(aq)

Ksp = 7.1 1012 = [Mg2+][OH]2
7.1 1012 = [x][2x]2
x = 1.2 104
2x = 2.4 104 = [OH]
pOH = log[OH] = log(2.4 104) = 3.62
pH = 14 3.62 = 10.38

45.

Fe(OH)2(s) U Fe2+(aq) + 2OH(aq)

ksp = 7.9 1016 = [Fe2+][OH]2
pH = 10.00
pOH = 14 10.00 = 4.00
[OH] = 104.00 = 1 104
7.9 1016 = [Fe2+][1 104]2
7.9 108 M = [Fe2+]
7.9 108 mol Fe 2+ 1 mol Fe(OH) 2
1

2+
gL =
1 L solution

1 mol Fe

46.

(a)

89.86 g Fe(OH) 2
1 mol Fe(OH) = 7.10 106 g L1

This is a limiting reagent problem.

0.100 mol Pb(NO3 ) 2

mL KI needed = 30.0 mL Pb(NO3)2

1000 mL Pb(NO3 ) 2 solution

1000 mL KI solution
2 mol KI

= 12.0 mL KI solution
0.500 mol KI

1 mol Pb(NO3 )2
20.0 mL KI solution is supplied. KI is in excess.

(b)

0.100 mol Pb(NO3 ) 2

g PbI2 = 30.0 mL Pb(NO3)2

1000 mL Pb(NO3 ) 2 solution

1 mol PbI 2 461.0 g PbI 2

= 1.38 g PbI2
1 mol Pb(NO3 ) 2 1 mol PbI 2
The concentration of the spectator ions:
[K+] = (0.500 M K+)(20.0 mL solution) 50.0 mL = 0.200 M K+
[NO3] = (0.100)(2)(30.0 mL solution) 50.0 mL = 0.12 M NO3
Total moles of I = (0.500 M I)(0.0200 L solution) = 0.0100 mol I
[I]:

2 mol I
0.100 mol Pb 2+
mol I used = 30.0 mL Pb2+ 1000 mL Pb 2+ solution 1 mol Pb 2+

= 6.00 103 mol I

[I] = (0.0100 mol I 6.00 103 mol I)/(0.050 L solution) = 0.0800 M I

[Pb ]: This will be the amount of Pb2+ that is in solution after the solid PbI2 reaches equilibrium
PbI2(s) U Pb2+(aq) + 2I(aq)
2+

447

Bringing It Together: Chapters 13 17

[Pb2+]

+x
x

I
C
E

[I]
0.0800 M
+x
0.0800 + x

Ksp = 7.9 109 = [Pb2+][I]2 = (x)(0.0800 + x)2

x << 0.0800
7.9 109 = (x)(0.0800)2
x = 1.23 106 M = [Pb2+]
47.

This is a simultaneous equilibrium problem.

CuCO3(s) U Cu2+(aq) + CO32(aq)
2+

Ksp = [Cu2+][CO32] =2.5 1010

2+

Cu (aq) + 4NH3(aq) U Cu(NH3)4 (aq)

Kform =

Cu ( NH ) 2 +
3 4

Cu

2+

NH3

= 1.1 1013

CuCO3(s) + 4NH3(aq) U Cu(NH3)42+(aq) + CO32(aq)

Cu ( NH ) 2 + CO 2
3 4
3

= 2.75 103
Koverall =
4
NH3

All of the Cu(NH3)42+ comes from the CuCO3

1 mol CuCO3
1
= 8.09 103
[Cu(NH3)42+] = 1.00 g CuCO3

123.6
g
CuCO
1.00
L
solution

As the Cu2+ is used to form Cu(NH3)42+, the [CO32] = [Cu(NH3)42+] = 8.09 103
Cu ( NH ) 2 + CO 2
8.09 103 8.09 103
3 4
3

3
2.75 10 =
=
4
4
x
NH

[ ]
3

x = 0.0124 M NH3
0.0124 mol NH3
mol NH3 = 1.00 L solution
=0.0124 mol NH3
1 L solution

48.

Assume the solution is saturated with CO2 and therefore the concentration of H2CO3 is 0.030 M
H2CO3 U 2H+ + CO32
2

11

K = Ka1 Ka2 = (4.3 10 )(4.7 10 ) = 2.0 10

17

H + CO32

=
H 2 CO3

First, calculate the [H+] at which thePbCO3 will begin to precipitate:

Ksp = 7.4 1014 = [Pb2+][CO32]
PbCO3(s) ' Pb2+(aq) + CO32(aq)
[Pb2+] = 0.010 M
[CO32] = (7.4 1014)/(0.010) = 7.4 1012 M

2.0 10 17 H CO 2
2.0 10 17 [ 0.030] 2
2 3
= 2.8 104
=
[H+] =
12

CO32
7.4 10

pH = 3.55

448

Bringing It Together: Chapters 13 17

Now, determine the [H+] at which the BaCO3 will begin to precipitate:
Ksp = 5.0 109 = [Ba2+][CO32]
BaCO3(s) U Ba2+(aq) + CO32(aq)
[Ba2+] = 0.010 M
[CO32] = (5.0 109)/(0.010) = 5.0 107 M

2.0 10 17 H CO 2
2.0 10 17 [ 0.030] 2
2 3
= 1.1 106
=
[H+] =
7

CO32
5.0 10

pH = 5.96

The pH range is between 3.55 and 5.96, above 5.96, BaCO3 will begin to precipitate.
49.

The less soluble substance is PbS. We need to determine the minimum [H+] at which NiS will precipitate.
Ni 2+ [ H 2S]
(0.100)(0.1)

K spa =
=
= 40
2
+
[H + ]2
H

[H + ] =

(from Table 17.2)

(0.10)(0.1)
= 0.016
40

pH = log[H+] = 1.80. At a pH lower than 1.80, PbS will precipitate and NiS will not. At larger values of
pH, both PbS and NiS will precipitate.
We also need to determine the [H+] at which PbS will start to precipitate
Pb 2+ [ H 2S]
(0.100)(0.1)

K spa =
=
= 3 107
(from Table 17.2)
2
+ 2
+
[H
]
H

[H + ] =

(0.10)(0.1)

= 182
3 107
pH = log[H+] = 2.26. Any acid in water will precipitate the PbS.
The pH range is 2.26 to 1.80 to allow the PbS to precipitate without the NiS.

50.

The less soluble substance is SnS. We need to determine the minimum [H2S] at which FeS will precipitate.
Fe 2+ [ H 2S]
(0.10) [ H 2S]

K spa =
=
= 600
(from Table 17.2)
2
+
[1 103 ]2
H

(600)(1 103 ) 2
= 6 103
(0.1)
The concentration of Sn2+ can now be determined.
Sn 2+ [ H 2S]
Sn 2+ 6 103

= 1 105
K spa =
=
2
3 2
+
[1
10
]

[ H 2 S] =

5
3 2
Sn 2+ = (1 10 )(1 10 ) = 1.7 109

(6 103 )

449

(from Table 17.2)

Bringing It Together: Chapters 13 17

51.

(a)

MS(s) U M2+(aq) + S2(aq)

Ksp = [M2+][S2] = 4.0 1029
MS(s) + H2O U M2+(aq) + HS2(aq) + OH(aq)
M 2+ [ H 2S]

Kspa =
= (4.0 1029)(1021) = 4.0 108
2
H+

(b)

x2

[0.30]

= 4.0 108

x = 6.0 105 M

450