Chemistry 192

Problem Set 6
Spring, 2018
Solutions

1. The solubility product of Al(OH)3 is 1.1 × 10−15 . Calculate the concentrations of

aluminum ions, hydroxide ions and hydronium ions in a saturated aqueous solution of
aluminum hydroxide.
Answer:
−
) Al3+
Al(OH)3(s) * (aq) + 3OH(aq)

Ksp = [Al3+ ][OH− ]3 = 1.1 × 10−15

[Al3+ ] [OH− ]
initial 0M 0M
change s 3s
equilibrium s M 3s M

27s4 = 1.1 × 10−15

s = [Al3+ ] = 8.0 × 10−5 M
[OH− ] = 3s = 2.4 × 10−4 M
1.00 × 10−14
[H3 O+ ] = = 4.2 × 10−11
2.4 × 10−4
2. The solubility product of Ag2 S is 1.6 × 10−49 . Calculate the molar solubility of silver
sulfide in water.
Answer:
) 2Ag+
Ag2 S(s) * 2−
(aq) + S(aq)

[Ag+ ] [S2− ]
initial 0M 0M
change 2s s
equilibrium 2s M s M

1
 (2s)2 s = 4s3 = 1.6 × 10−49

s = molar solubility = 3.4 × 10−17 M

3. The solubility of Ag3 AsO4 in water is 8.5 ×10−4 g mL−1 . Calculate the solubility
product of silver arsenate.
Answer:
) 3Ag+
Ag3 AsO4(s) * 3−
(aq) + AsO4(aq)

8.5 × 10−4 g
moles dissolved of silver arsenate = = 1.8 × 10−6 mol
463 g mol−1
1.8 × 10−6 mol
[AsO3−
4 ] = = 1.8 × 10−3 M
0.00100 L
−3
[Ag+ ] = 3[AsO3−
4 ] = 5.5 × 10 M
Ksp = (5.5 × 10−3 )3 (1.8 × 10−3 ) = 3.1 × 10−10

4. The solubility product of Ag2 CO3 is Ksp = 5.0 × 10−12 . Calculate the molar solubility
of silver carbonate in a) water and b) a 0.20 M aqueous AgNO3 solution (silver nitrate
is 100% ionized).
Answer:
) 2Ag+
Ag2 CO3(s) * 2−
(aq) + CO3(aq)

[Ag+ ] [CO2−3 ]
initial 0M 0M
(a)
change 2s s
equilibrium 2s M sM

−12
[Ag+ ]2 [CO2− 3
3 ] = 4s = 5.0 × 10

−4
s = solubility = [CO2−
3 ] = 1.1 × 10 M
[Ag+ ] [CO2−3 ]
initial 0.20 M 0M
(b)
change 2s s
equilibrium (0.20 + 2s) M sM

s(0.20 + 2s)2 ≈ s(0.20)2 = 5.0 × 10−12

solubility = s = 1.3 × 10−10 M

2
5. The solubility product of AgCl is Ksp = 1.1 × 10−10 . Calculate the weight of silver
nitrate that must be added to 10. mL of a 0.10 M sodium chloride solution to initiate
the silver chloride precipitation reaction.
Answer:
[Ag+ ][Cl− ] = 1.1 × 10−10
1.1 × 10−10
[Ag+ ] = = 1.1 × 10−9 M
0.10
(1.1 × 10−9 mol L−1 )(0.010 L) = 1.1 × 10−11 mol
(1.1 × 10−11 mol)(170. g mol−1 ) = 1.9 × 10−9 g

6. The solubility product of Ag2 SO4 is 7.0 × 10−5 . A laboratory student mixes 10. mL of
a 0.010 M silver nitrate solution with 10. mL of a 0.020 M sodium sulfate (Na2 SO4 )
solution. Calculate a suitable reaction quotient to determine if silver sulfate precipitate
should form when the two solutions are mixed.
Answer:
) 2Ag+
Ag2 SO4(s) * 2−
(aq) + SO4(aq)

[Ag+ ] = 0.0050 M [SO2−

4 ] = 0.010 M
−7
Q = [Ag+ ]2 [SO2− 2
4 ] = (0.0050) (0.010) = 2.5 × 10 < Ksp
No precipitation.

7. The solubility product of Cu(OH)2 is 1.0 × 10−16 . Calculate

(a) the pH of a saturated solution of copper (II) hydroxide in water;

Answer:
−
Cu(OH)2(s) * ) Cu2+(aq) + 2HO(aq)

Ksp = [Cu2+ ][OH− ]2

[Cu2+ ] [OH− ]
initial 0M 0M
change s 2s
equilibrium sM 2s M

4s3 = 1.0 × 10−16 s = 2.9 × 10−6 [OH− ] = 2s = 5.8 × 10−6

pOH = − log10 (5.8 × 10−6 ) = 5.23 pH = 14.00 − pOH = 8.77

(b) the molar solubility of copper (II) hydroxide in a solution having pH=1.00;
Answer:
1.00 × 10−14
[OH− ] = = 1.00 × 10−13
1.00 × 10−1

3
 1.0 × 10−16
[Cu2+ ] = = 1.0 × 1010
(1.00 × 10−13 )2
i.e. completely soluble.
(c) the molar solubility of copper (II) hydroxide in a solution having pH=13.00.
Answer:
[OH− ] = 0.10 M
1.0 × 1)−16
[Cu2+ ] = = 1.0 × 10−14 M
(0.10)2
8. Problem 54, page 814 textbook.
Answer:
1 1
Cu(NH3 )2+ * 2+
4(aq) ) Cu(aq) + 4NH3(aq) K= = 13
= 9.1 × 10−14
Kf 1.1 × 10

[Cu(NH3 )2+
2 ] [Cu2+ ] [NH3 ]
initial 0.10 M 0M 6.0-0.40 = 5.6 M
change -x x 4x
equilibrium (0.10 − x) M xM (5.6 + 4x) M

[Cu2+ ][NH3 ]4 x(5.6 + x)4 x(5.6)4

= ≈ = 9.1 × 10−14
[Cu(NH3 )2+
4 ] 0.10 − x 0.10

x = [Cu2+ ] = 9.2 × 10−18 M

9. Problem 56, page 814 textbook.

Answer:
As in problem 8
1 1
Cu(NH3 )2+ * 2+
4(aq) ) Cu(aq) + 4NH3(aq) K= = = 9.1 × 10−14
Kf 1.1 × 1013

[Cu2+ ][NH3 ]4 [Cu2+ ](0.10)4

= = 9.1 × 10−14
[Cu(NH3 )2+
4 ] 0.015
[Cu2+ ] = 1.4 × 10−11 M
−
) NH+
NH3(aq) + H2 O(`) * 4(aq) OH(aq)
−
[NH+4 ][OH ]
= 1.8 × 10−5
[NH3 ]

4
 [NH3 ] [NH+4] [OH− ]
initial 0.10 M 0.10 M 0M
change -x x x
equilibrium (0.10 − x) M (0.10 + x) M xM

(0.10 + x)x
≈ x = 1.8 × 10−5 = [OH− ]
0.10 − x
−
) Cu2+
Cu(OH)2(s) * (aq) + 2OH(aq)

Q = [Cu2+ ][OH− ]2 = (1.4 × 10−11 )(1.8 × 10−5 )2

= 4.5 × 10−21 < Ksp
No precipitate.

10. Aqueous silver ions form a coordination complex with thiosulfate anions according to
the reaction
Ag+ 2− * 3−
(aq) + 2S2 O3(aq) ) Ag(S2 O3 )2(aq) ,

where the formation equilibrium constant for the complex is Kf = 1.7 × 1013 . Given
the solubility product of silver iodide, AgI, is Ksp = 8.5 × 10−17 , calculate the molar
solubility of silver iodide in a solution that is 0.100 M in thiosulfate.
Answer:
−
) Ag+
AgI(s) * (aq) + I(aq) Ksp = 8.5 × 10−17
Ag+ 2− * 3−
(aq) + 2S2 O3(aq) ) Ag(S2 O3 )2(aq) Kf = 1.7 × 1013
−
AgI(s) + 2S2 O2− * 3−
3(aq) ) Ag(S2 O3 )2(aq) + I(aq) K = Ksp Kf = 1.4 × 10−3

[S2 O2−
3 ] [Ag(S2 O3 )3−
2 ] [I− ]
initial 0.100 M 0M 0M
change -2y y y
equilibrium (0.100 − 2y) M yM yM

y2
2
= 1.4 × 10−3
(0.100 − 2y)
y
= 3.7 × 10−3
0.100 − 2y
y = 3.4 × 10−3 M

5
11. Zinc ions form a complex in cyanide solutions according to the reaction
− 2−
Zn2+ *
(aq) + 4CN(aq) ) Zn(CN)4(aq)

with a formation constant Kf = 1.0 × 1018 . It is found that the solubility of solid zinc
selenide (ZnSe) in a 0.100 M cyanide solution is 6.0 × 10−5 M. Calculate the solubility
of zinc selenide in water.
Answer:
2−
ZnSe(s) + 4CN− * 2−
(aq) ) Zn(CN)4(aq) + Se(aq)

[CN− ] [Zn(CN)2−
4 ] [Se2− ]
initial 0.100 M 0M 0M
change -4(6.0 × 10−5 ) M 6.0 × 10−5 M 6.0 × 10−5 M
equilibrium 0.100 M 6.0 × 10−5 M 6.0 × 10−5 M

(6.0 × 10−5 )2
K= = 3.6 × 10−5
(0.100)4

= Ksp Kf = 1.0 × 1018 Ksp

Ksp = 3.6 × 10−23
) Zn2+
ZnSe(s) * 2−
(aq) + Se(aq)

[Zn2+ ] [Se2− ]
initial 0M 0M
change sM sM
equilibrium s M sM

s2 = 3.6 × 10−23

s = 6.0 × 10−12 M

12. The silver cyanide coordination complex, Ag(CN)−

2 forms by the reaction

− −
Ag+ *
(aq) + 2CN(aq) ) Ag(CN)2(aq)

with associated equilibrium constant Kf = 5.6 × 1018 . Given the solubility product of
silver iodide (AgI) is Ksp = 8.5 × 10−17 , calculate the solubility of silver iodide in a
solution having [CN− ]=0.500 M.
Answer:
−
AgI(s) + 2CN− * −
(aq) ) Ag(CN)2(aq) + I(aq)

K = Kf Ksp = 5.6 × 1018 × 8.5 × 10−17 = 4.8 × 102

6
 [CN− ] [Ag(CN)−
2] [I− ]
initial 0.500 M 0M 0M
change -2s s s
equilibrium (0.500 − 2s) M sM sM

2 [Ag(CN)− −
2 ][I ] s2
4.8 × 10 = =
[CN− ]2 (0.500 − 2s)2
s
= 22. s = 11. − 44.s s = 0.24 M
0.500 − 2s
13. Zinc ions form a coordination complex in aqueous ammonia

Zn2+ * 2+
(aq) + 4NH3(aq) ) Zn(NH3 )4(aq)

having formation equilibrium constant Kf = 4.1 × 108 . Zinc sulfide (ZnS) is only spar-
ingly soluble in water with solubility product constant Ksp = 2.0×10−25 . Calculate the
molar solubility of zinc sulfide in a 0.10 M aqueous ammonia solution. Approximations
work for this system.
Answer:
2−
ZnS(s) + 4NH3(aq) * ) Zn(NH3 )2+
4(aq) + S(aq)
2−
[Zn(NH3 )2+
4 ][S ]
K = Kf Ksp = 8.2 × 10−17 =
[NH3 ]4

[NH3 ] [Zn(NH3 )2+ 2−

4 ] [S ]
initial 0.10 M 0M 0M
change −4s s s
equilibrium (0.10 − 4s) M sM sM

s2 s2
8.2 × 10−17 = ≈
(0.10 − 4s)4 1.0 × 10−4

s = 9.1 × 10−11 M

14. Silver ions (Ag+ ) react with thiocyanate ions (SCN− ) in aqueous solution to form the
coordination complex Ag(SCN)3− 10
4 with associated formation constant Kf = 1.2 × 10 .
Consider a solution that is made by adding 0.050 moles of silver ions to 0.250 L of
a 2.50 M thiocyanate solution. Calculate the concentration of free silver ions (Ag+ )
when equilibrium is reached. Approximations work for this problem.
Answer
+ −
Ag(SCN)3− *
4(aq) ) Ag(aq) + 4SCN(aq)

7
 1
K= = 8.3 × 10−11
Kf
Initially
0.050 mol
[Ag(SCN)3−
4 ] = = 0.20 M
0.250 L

[Ag(SCN)3−4 ] [Ag+ ] [SCN− ]

initial 0.20 M 0 M (2.50-4(0.20))=1.70 M
change -y y 4y
equilibrium (0.20 − y) M yM (1.70 + 4y) M

[Ag+ ][SCN− ]4 y(1.70 + 4y)4 y(1.70)4

8.3 × 10−11 = = ≈
[Ag(SCN)−4]
(0.20 − y) 0.20

y = [Ag+ ] = 2.0 × 10−12 M

15. The formation equilibrium constant for the cobalt ammonia complex [Co(NH3 )3+ 6 ] is
33 3+
Kf = 4.5 × 10 . Calculate the molar concentration of free Co(aq) in a solution made
by mixing 0.100 L of 0.0500 M Co3+ to 0.500 L of 0.250 M aqueous ammonia. Approx-
imations work for this problem.
Answer:
1
Co(NH3 )3+ * 3+
6(aq) ) Co(aq) + 6NH3(aq) K= = 2.2 × 10−34
Kf

We assume initially all the cobalt ions are in the form of the complex. The initial
concentrations are found using

nCo3+ = (0.0500 mol L−1 )(0.100 L) = 5.00 × 10−3 mol

Before complexation

nN H3 = (0.250 mol L−1 )(0.500 L) = 0.125 mol

After complexation

nN H3 = 0.125 mol − 6(5.00 × 10−3 mol) = 0.095 mol

5.00 × 10−3 mol

[Co(NH3 )3+
6 ] = = 8.33 × 10−3 M
0.600 L
0.095 mol
[NH3 ] = = 0.16 M
0.600 L

8
 [Co(NH3 )3+
6 ] [Co3+ ] [NH3 ]
initial 8.33 ×10−3 M 0M 0.16 M
change -y y 6y
equilibrium (8.33 × 10−3 − y) M y M (0.16 + 6y) M

−34 [Co3+ ][NH3 ]6 y(0.16 + 6y)6 y(0.16)6

2.2 × 10 = = ≈
[Co(NH3 )3+
6 ] 8.33 × 10−3 − y 8.33 × 10−3
y = [Co3+ ] = 1.2 × 10−31 M
16. The solubility product constant for zinc oxalate (ZnC2 O4 ) is 2.7 × 10−8 and the for-
mation constant for the zinc cyanide coordination complex [Zn(CN)2− 18
4 ] is 1.0 × 10 .
Consider a mixture that is formed by combing 0.25 L of a 1.0 × 10−4 M CN− solution
and 0.35 L of a 6.0 × 10−6 M Zn2+ solution. After the solutions are mixed 0.50 moles
of oxalate ions are added to the solution. Assuming the added oxalate does not change
the total volume of the solution, determine if a zinc oxalate precipitate will form. Ap-
proximations work for this problem.
Answer: Before complex formation
nCN − = (1.0 × 10−4 mol L−1 )(0.25 L) = 2.5 × 10−5 mol
nZn2+ = (6.0 × 10−6 mol L−1 )(0.35 L) = 2.1 × 10−6 mol
After complex formation
nCN − = 2.5 × 10−5 mol − 4(2.1 × 10−6 mol) = 1.7 × 10−5 mol
− 1.7 × 10−5 mol −5 2− 2.1 × 10−6 mol
[CN ] = = 2.8×10 M [Zn(CN)4 ] = = 3.5×10−6 M
0.60 L 0.60L
1 [Zn2+ ][CN− ]4
Zn(CN)2− *
4(aq) ) Zn2+
(aq) + 4CN −
(aq) K = = 1.0 × 10−18
=
Kf [Zn(CN)2−4 ]

[Zn(CN)2−4 ] [Zn2+ ] [CN− ]]

−6
initial 3.5 ×10 M 0M 2.8 × 10−5 M
change -y y 4y
equilibrium (3.5 × 10−6 − y) M y M (2.8 × 10−5 + 4y) M

y(2.8 × 10−5 + 4y)4 y(2.8 × 10−5 )4

1.0 × 10−18 = ≈
2.5 × 10−6 − y 3.5 × 10−6
y = [Zn2+ ] = 1.4 × 10−5 M
0.50 mol
[C2 O2−
4 ] = = 0.83 M
0.60 L
−5 −5
Q = [Zn2+ ][C2 O2−
4 ] = (1.4 × 10 )(0.83) = 1.2 × 10 > Ksp
Precipitate forms