Fundamentals of Analytical Chemistry: 8th ed.

Chapter 11

Chapter 11

11-1 The overall dissociation constant for H2S is

[ H 3O + ]2 [S 2- ]
= K1 K 2
[ H 2S]

In a solution saturated with the gas, [H2S] is constant, therefore

[ H 2S] K
[S 2- ] = K1 K 2 or [S 2- ] =
[ H 3 O + ]2 [ H 3 O + ]2

11-2 The simplifications in equilibrium calculations involve assuming that the concentrations

of one or more species can be approximated as 0.00 M. Adding or subtracting a

concentration that can be approximated as 0.00 leads to a meaningful result. In contrast,

multiplying or dividing by 0.00 in the equilibrium constant expression causes the

constant to become equal to zero or infinity. Thus, the expression is meaningless.

11-3 A charge-balance equation is derived by relating the concentration of cations and anions

such that

no. mol/L positive charge = no. mol/L negative charge

For a doubly charged ion, such as Ba2+, the concentration electrons for each mole is twice

the molar concentration of the Ba2+. That is,

mol/L positive charge = 2[Ba2+]

Thus, the molar concentration of all multiply charged species is always multiplied by the

charge in a charge-balance equation.

11-4 (a) 0.20 = [H3AsO4] + [H2AsO4-] + [HAsO42-] + [AsO43-]

(b) 0.10 = [H3AsO4] + [H2AsO4-] + [HAsO42-] + [AsO43-]

2(0.10) = [Na+] = 0.20

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

(c) 0.0500 + 0.100 = [ClO-] + [HClO]

0.100 = [Na+]

(d) [F-] + [HF] = 0.25 + 2[Ca2+]

[Na+] = 0.25

(e) 0.100 = [Na+] = [OH-] + 2[Zn(OH)42-]

(f) [Ba2+] = [C2O42-] + [HC2O4-] + [H2C2O4]

(g) [Ca2+] = ½([F-] + [HF])

11-5 (a) [H3O+] = [OH-] + [H2AsO4-] + 2[HAsO42-] + 3[AsO43-]

(b) [Na+] + [H3O+] = [OH-] + [H2AsO4-] + 2[HAsO42-] + 3[AsO43-]

(c) [Na+] + [H3O+] = [OH-] + [ClO-]

(d) [Na+] + [H3O+]+ 2[Ca2+] = [F-] + [OH-]

(e) 2[Zn2+] + [Na+] + [H3O+] = [OH-] + 2[Zn(OH)42-]

(f) 2[Ba2+] + [H3O+] = [OH-] + 2[C2O42-] + [HC2O4-]

(g) 2[Ca2+] + [H3O+] = [OH-] + [F-]

11-6 Step 1 Ag2C2O4 ' 2Ag+ + C2O42-

H2C2O4 + H2O ' H3O+ + HC2O4-

HC2O4- + H2O ' H3O+ + C2O42-

Step 2 S = solubility = [Ag+]/2

Step 3 [Ag+]2[C2O42-] = Ksp = 3.5×10-11 (1)

[ H 3O + ][ HC 2 O -4 ]
= K1 = 5.60 × 10 −2 (2)
[H 2 C 2 O 4 ]

[ H 3O + ][C 2 O 24- ]
= K 2 = 5.42 × 10 −5 (3)
[ HC 2 O -4 ]

Step 4 [Ag+] = 2([C2O42-] + [HC2O4-] + [H2C2O4]) (4)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

[H3O+] = 1.0 × 10-6 (5)

Step 5 No charge-balance equation because a buffer of unknown composition is present.

Step 6 Unknowns: [Ag+], [C2O42-], [HC2O4-], [H2C2O4]

Equations: (1), (2), (3) and (4)

Step 7 No approximations needed.

Step 8 Substituting (5) into (3) and rearranging gives

[HC2O4-] =
[
1.0 × 10 −6 C 2 O 24- ] = 0.01845[C2O42-]
5.42 × 10 −5

Substituting this relationship and (5) into (2) and rearranging gives

[H2C2O4] =
[
1.0 × 10 −6 × 0.01845 C 2 O 24- ] = 3.29×10-7[C2O42-]
5.60 × 10 − 2

Substituting these two relationships into (4) gives

[Ag+] = 2[C2O42-] + 2×(0.01845[C2O42-]) + 2×(3.29×10-7[C2O42-])

[Ag+] = 2.037[C2O42-] or

[C2O42-] = 0.4909[Ag+]

Substituting this relationship into (1) and rearranging gives

[Ag+] = (3.5×10-11/0.4909)1/3 = 4.15×10-4 M

Finally

S = 4.15×10-4/2 = 2.1×10-4

Substituting other values for [H3O+] yields the following solubility data:
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

[H3O+], M Solubility, M

(a) 1.0×10-6 2.1×10-4

(b) 1.0×10-7 2.1×10-4

(c) 1.0×10-9 2.1×10-4

(d) 1.0×10-11 2.1×10-4

11-7 Proceeding as in Problem 11-6, we write

BaSO4 ' Ba2+ + SO42- Ksp = 1.1×10-10

HSO4- + H2O ' H3O+ + SO42- K2 = 1.02×10-2

S = [Ba2+]

[Ba2+][SO42-] = 1.1×10-10 (1)

[ H 3O + ][SO 24− ]
= 1.02×10-2 (2)
[ HSO 4− ]

Mass balance requires that

[Ba2+] = [SO42-] + [HSO4-] (3)

[H3O+] = 2.5 (4)

Substituting (4) into (2) gives upon rearranging

[HSO4-] = (2.5)[SO42-]/(1.02×10-2) = 245.1[SO42-] (5)

Substituting (5) into (3) gives

[Ba2+] = [SO42-] + 245.1[SO42-] = 246.1[SO42-] (6)

Substituting (6) into (1) gives

246.1[SO42-]2 = 1.1×10-10

[SO42-] = 6.7×10-7 M

From (6) [Ba2+] = 1.6×10-4 M = S

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

Proceeding in a similar manner for the other [H3O+] gives

[H3O+] S, mol/L

(a) 2.5 1.65×10-4

(b) 1.5 1.28×10-4

(c) 0.060 2.75×10-5

(d) 0.200 4.76×10-5

11-8 The following derivation applies to this and the following two problems.

MS(s) ' M2+ + S2-

H2S + H2O ' H3O+ + HS- K1 = 9.6×10-8

HS- + H2O- ' H3O+ + S2- K2 = 1.3×10-14

H2S + 2H2O ' 2H3O+ + S2- K1K2 = 9.6×10-8 × 1.3×10-14 = 1.25×10-21

S = solubility = [M2+] = [S2-] + [HS-] + [H2S]

[M2+][S2-] = Ksp (1)

[ H 3O + ][ HS − ]
= K2 = 1.3×10-14 (2)
[H 2S]

[ H 3O + ]2 [S 2− ]
= K1K2 = 1.25×10-21 (3)
[H 2S]
From mass-balance consideration

[M2+] = [S2-] + [HS-] + [H2S] (4)

Substituting (2) and (3) into (4) gives

[ H 3O + ][S 2− ] [ H 3O + ]2 [S 2− ] ⎛ [ H O + ] [ H 3 O + ]2 ⎞
[M2+] = [S2-] + + = [S 2− ]⎜⎜1 + 3 + ⎟ (5)
K2 K1 K 2 ⎝ K2 K1 K 2 ⎟⎠

Substituting (1) into (5)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

K sp ⎛ [ H 3O + ] [ H 3O + ]2 ⎞
[M2+] = ⎜1 + + ⎟
[ M 2+ ] ⎜⎝ K2 K1 K 2 ⎟⎠

⎛ [ H O + ] [ H 3 O + ]2 ⎞
[M2+] = K sp ⎜⎜1 + 3 + ⎟
⎝ K2 K1 K 2 ⎟⎠

⎛ [ H 3O + ] [ H 3 O + ]2 ⎞
[M2+] = K sp ⎜⎜1 + + ⎟ (6)
⎝ 1.3 × 10
−14
1.25 × 10 −21 ⎟⎠

(a) Substituting Ksp = 8×10-37 and [H3O+] = 2.0×10-1 into (6) gives

[M2+] = solubility =
⎛
8 ×10 −37 ⎜⎜1 +
0.20
+
(0.20)2 ⎞⎟
⎝ 1.3 ×10
−14
1.25 ×10 −21 ⎟⎠

= 5.1 × 10 −9 M

(b) Substituting Ksp = 8×10-37 and [H3O+] = 2.0×10-4 into (6) gives

solubility = 5.1 × 10 −12 M

11-9 (a) Substituting Ksp = 1×10-27 and [H3O+] = 2.0×10-1 into (6) gives

solubility = 2 × 10 −4 M

(b) Substituting Ksp = 1×10-27 and [H3O+] = 2.0×10-4 into (6) gives

solubility = 2×10-7 M

11-10 (a) Substituting Ksp = 3×10-14 and [H3O+] = 2.0×10-5 into (6) gives

solubility = 0.1 M

(b) Substituting Ksp = 3×10-14 and [H3O+] = 2.0×10-7 into (6) gives

solubility = 1×10-3 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

11-11 PbCO3 ' Pb2+ + CO32- Ksp = [Pb2+][CO32-] = 7.4×10-14

[ H 3O + ][ HCO -3 ]
H2CO3 + H2O ' H3O+ + HCO3- K1 = = 4.45×10-7
[ H 2 CO 3 ]

[ H 3O + ][CO 32- ]
HCO3 + H2O ' H3O + CO3
- + 2-
K2 = −
= 4.69×10-11
[ HCO 3 ]

[Pb2+] = [CO32-] + [HCO3-] + [H2CO3]

[H3O+] = 1×10-7

Proceeding as in problem 11-8

⎛ [ H O + ] [ H 3 O + ]2 ⎞
[M2+] = K sp ⎜⎜1 + 3 + ⎟
⎝ K2 K1 K 2 ⎟⎠

2+
[Pb ] = 7.4 ×10 −14
⎛ −7
⎜1 + 1.0 ×10 + (
1.0 ×10 −7 )
2
⎞
⎟
⎜ 4.69 ×10 −11
4 .45 × 10 − 7
× 4. 69 × 10 −11 ⎟
⎝ ⎠

solubility = [Pb2+] = 1.4×10-5 M

11-12 Ag2SO3 ' 2Ag+ + SO32- Ksp = [Ag+]2[SO32-] = 1.5×10-14 (1)

[ H 3O + ][ HSO -3 ]
H2SO3 + H2O ' H3O+ + HSO3- K1 = = 1.23×10-2 (2)
[ H 2SO 3 ]

[ H 3O + ][SO 32- ]
HSO3- + H2O ' H3O+ + SO32- K2 = −
= 6.6×10-8 (3)
[ HSO 3 ]

[ H 3O + ]2 [SO 32- ]
H2SO3 + 2H2O ' 2H3O+ + SO32- K1K2 = = 8.1×10-10 (4)
[ H 2SO 3 ]

The mass balances are

½ [Ag+] = [SO32-] + [HSO3-] + [H2SO3] (5)

[H3O+] = 1×10-8 (6)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

Substituting (2), (4) and (6) into (5) gives

½ [Ag+] = [SO32-] +
(1 × 10 ) [SO
−8 2-
3 ]
+
(1 × 10 ) [SO
−8 2 2-
3 ]
6.6 × 10 -8
8.1 × 10 -10

⎛
½ [Ag+] = [SO32-] ⎜1 +
1 × 10 −8
+
(1 × 10 −8 )2 ⎞⎟
⎜ 6.6 × 10 -8 8.1 × 10 −10 ⎟⎠
⎝

Substituting (1) into this expression gives

+
½ [Ag ] =
K sp ⎛
⎜ 1+
1 × 10 −8
+
(1 × 10 −8 ) ⎞⎟
2

[2
]
Ag + ⎜⎝ 6.6 × 10
-8
8.1 × 10 −10 ⎟⎠

+ 3
[Ag ] = 2×1.5×10
⎛
-14 ⎜
1+
1 × 10 −8
+
(1 × 10 −8 ) ⎞⎟
2

⎜ 6.6 × 10 -8
8.1 × 10 −10 ⎟⎠
⎝

[Ag+] = 4.2×10-5

Solubility = 2.1×10-5 M

11-13 [Cu2+][OH-]2 = 4.8×10-20 [Mn2+][OH-]2 = 2×10-13

(a) Cu(OH)2 precipitates first

(b) Cu2+ begins to precipitate when

[OH-] = 4.8 × 10 −20 / 0.050 = 9.8×10-10 M

(c) Mn2+ begins to precipitate when

[OH-] = 2 × 10 −13 / 0.040 = 2.2×10-6

[Cu2+] = 4.8×10-20/(2.2×10-6)2 = 9.6×10-9 M

11-14 Ba(IO3)2 ' Ba2+ + 2IO3- Ksp = 1.57×10-9

BaSO4 ' Ba2+ + SO42- Ksp = 1.3×10-10

To initiate precipitation of Ba(IO3)2

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

[Ba2+] = 1.57×10-9/(0.050)2 = 6.3×10-7

To initiate precipitation of BaSO4

[Ba2+] = 1.3×10-10/(0.040) = 3.2×10-9 M

(a) BaSO4 precipitates first

(b) [Ba2+] = 3.2×10-9 M

(c) When [Ba2+] = 6.3×10-7 M

[SO42-] = 1.1×10-10/(6.3×10-7) = 1.7×10-4 M

11-15 (a) [Ag+] = Ksp/[I-] = 8.3×10-17/(1.0×10-6) = 8.3×10-11 M

(b) [Ag+] = Ksp/[SCN-] = 1.1×10-12/(0.070) = 1.6×10-11 M

(c) [I-] when [Ag+] = 1.6×10-11 M

[I-] = 8.3×10-17/(1.6×10-11) = 5.2×10-6 M

[SCN-]/[I-] = 0.070/(5.2×10-6) = 1.3×104

(d) [I-] = 8.3×10-17/(1.0×10-3) = 8.3×10-14 M

[SCN-] = 1.1×10-12/(1.0×10-3) = 1.1×10-9 M

[SCN-]/[I-] = 1.1×10-9/(8.3×10-14) = 1.3×104

Note that this ratio is independent of [Ag+] as long as some AgSCN(s) is present.

11-16 (a) [Ba2+][SO42-] = 1.1×10-10 [Sr2+][SO42-] = 3.2×10-7

BaSO4 precipitation is complete when

[SO42-] = 1.1×10-10/(1.0×10-6) = 1.1×10-4 M

SrSO4 begins to precipitate when

[SO42-] = 3.2×10-7/(0.050) = 6.4×10-6 M

SrSO4 begins to precipitate before the Ba2+ concentration is reduced to 1.0×10-6 M.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

(b) [Ba2+][SO42-] = 1.1×10-10 [Ag+]2[SO42-] = 1.6×10-5

BaSO4 precipitation is complete when [SO42-] = 1.1×10-4 M

Ag2SO4 begins to precipitate when

[SO42-] = 1.6×10-5/(0.020)2 = 0.040 M

Ag2SO4 does not precipitate before the Ba2+ concentration is reduced to 1.0×10-6 M.

(c) Be2+ precipitates when [OH-] = (7.0×10-22/(0.020))1/2 = 1.9×10-10 M

Hf4+ precipitates when [OH-] = (4.0×10-26/(0.010))1/4 = 1.4×10-6 M

Be precipitation complete when [OH-] = (7.0×10-22/1.0×10-6)1/2 = 2.6×10-8 M

Hf(OH)4 does not precipitate before the Be2+ concentration is reduced to 1.0×10-6 M.

(d) In3+ precipitates when [IO3-] = (3.3×10-11/(0.20))1/3 = 5.5×10-4 M

Tl+ precipitates when [IO3-] = 3.1×10-6/(0.090) = 3.4×10-5 M

Tl+ precipitation complete when [IO3-] = 3.1×10-6/1.0×10-6 = 3.1 M

In(IO3)3 begins to precipitate before the Tl+ concentration is reduced to 1.0×10-6 M.

11-17 AgBr ' Ag+ + Br- 5.0×10-13 = [Ag+][Br-] (1)

[ Ag(CN ) 2− ]
Ag+ + 2CN- ' Ag(CN)2- 1.3×1021 = (2)
[ Ag + ][CN − ]2

It is readily shown that the reaction

CN- + H2O ' HCN + OH-

proceeds to such a small extent that it can be neglected in formulating a solution to this

problem. That is, [HCN] << [CN-], and only the equilibria shown need to be taken into

account.

Solubility = [Br-]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

Mass balance requires that

[Br-] = [Ag+] + [Ag(CN)2-] (3)

0.100 = [CN-] + 2[Ag(CN)2-] (4)

We now have 4 equations and 4 unknowns.

Based upon the large size of β2 let us assume that

[CN-] << 2[Ag(CN)2-] and [Ag+] << [Ag(CN)2-]

(4) becomes [Ag(CN)2-] = 0.100/2 = 0.0500

and (3) becomes [Br-] = [Ag(CN)2-] = 0.0500

To check the assumptions, we calculate [Ag+] by substituting into (1)

[Ag+] = 5.0×10-13/0.0500 ≅ 1×10-11 (9 1×10-11 << 0.0500)

To obtain [CN-] we substitute into (2) and rearrange

0.0500
[CN-] = = 2.0×10-6 (9 2×10-6 << 0.100)
(1× 10 )(1.3 × 10 21 )
−11

Thus, the two assumptions are valid and

Solubility = [Br-] = 0.0500 M

mmol 0.1877 g AgBr

mass AgBr/200 mL = 0.0500 × 200 mL ×
mL mmol AgBr

= 1.877 g

11-18 CuCl(s) ' Cu+ + Cl- Ksp = [Cu+][Cl-] = 1.9×10-7 (1)

[CuCl -2 ]
Cu+ + 2Cl- ' CuCl2- β2 = = 7.9×104 (2)
[Cu + ][Cl - ]2

It is convenient to multiply (1) by (2) to give

[CuCl -2 ]
= 1.9×10-7×7.9×104 = 1.5×10-2 (3)
[Cl - ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

From a charge balance consideration, we can write (if we assume [H3O+] = [OH-])

[Cu+] + [Na+] = [Cl-] + [CuCl2-] (4)

By rearranging (1) and (3) and substituting into (4) we obtain

1.9 × 10 −7
[Cl-] = [Na+] + - 1.5×10-2[Cl-]
[Cl - ]

which rearranges to the quadratic

0 = 1.015[Cl-]2 - [Na+][Cl-] - 1.9×10-7 (5)

By using [Na+] = the NaCl analytical concentration, (5) can be solved to give the

following [Cl-]

(a) 2.0 M (c) 0.020 M (e) 5.4×10-4 M

(b) 0.20 M (d) 0.0021 M

Note that the equilibrium [Cl-] concentration is larger than the NaCl analytical

concentration for parts (d) and (e). The reason for this apparent anomaly is that the

dissolution of CuCl to give Cu+ and Cl- contributes significantly to the equilibrium [Cl-]

at the lower NaCl analytical concentrations.

The solubility of CuCl can be obtained from the calculated [Cl-] and the expression

1.9 × 10 −7
S = [Cu+] + [CuCl2-] = + 1.5×10-2[Cl-]
[Cl − ]

Solution of this equation for each of the [Cl-] gives

(a) 0.030 M (c) 3.1×10-4 M (e) 3.6×10-4 M

(b) 3.0×10-3 M (d) 1.2×10-4 M

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

11-19 (a) CaSO4(s) ' Ca2+ + SO42- Ksp = [Ca2+][SO42-] = 2.6×10-5 (1)

[Ca 2+ ][SO 24- ]

CaSO4(aq) ' Ca2+ + SO42- Kd = = 5.2×10-3 (2)
[CaSO 4 ( aq)]

CaSO4(s) ' CaSO4(aq) (3)

The mass balance gives

[Ca2+] = [SO42-] (4)

We have 3 equations and 3 unknowns ([Ca2+], [SO42-], and [CaSO4(aq)]

To solve we divide (1) by (2) to give

[CaSO4(aq)] = Ksp/Kd = (2.6×10-5)/(5.2×10-3) = 5.0×10-3

Note that this is the equilibrium constant expression for (3) and indicates that the

concentration of un-ionized CaSO4 is always the same in a saturated solution of CaSO4.

Substituting (4) into (1) gives

[Ca2+] = (2.6×10-5)1/2 = 5.1×10-3

and since S = [CaSO4(aq)] + [Ca2+] we obtain

S = 5.0×10-3 + 5.1×10-3 = 0.0101 M

%CaSO4(aq) = (5.0×10-3/1.01×10-2)×100% = 49%

(b) (Note: In the first printing of the text, the answer in the back of the book was in error.)

Here [CaSO4(aq)] is again equal to 5.0×10-3 and the mass balance gives

[SO42-] = 0.0100 + [Ca2+] (5)

Substituting (1) into (5) and rearranging gives

0 = [SO42-]2 - 0.0100[SO42-] - Ksp

which may be solved using the quadratic equation to give

[SO42-] = 0.0121 and [Ca2+] = 2.14×10-3

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

S = 5.0×10-3 + 2.14×10-3 = 7.14×10-3

%CaSO4(aq) = (5.0×10-3/7.14×10-3)×100% = 70%