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# Fundamentals of Analytical Chemistry: 8th ed.

Chapter 11

Chapter 11

[ H 3O ]2 [S2- ]
K1 K 2
[ H 2S]

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

[ H 2S] K
[S2- ] K1 K 2 or [S2- ]
[ H 3 O ]2 [ H 3 O ]2

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

## 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

## mol/L positive charge = 2[Ba2+]

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

## 2(0.10) = [Na+] = 0.20

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

0.100 = [Na+]

[Na+] = 0.25

## Step 3 [Ag+]2[C2O42-] = Ksp = 3.510-11 (1)

[ H 3O ][ HC 2 O -4 ]
K1 5.60 10 2 (2)
H 2C 2O 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

## 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- = 3.2910-7[C2O42-]
5.60 10 2

## [Ag+] = 2[C2O42-] + 2(0.01845[C2O42-]) + 2(3.2910-7[C2O42-])

[Ag+] = 2.037[C2O42-] or

[C2O42-] = 0.4909[Ag+]

## [Ag+] = (3.510-11/0.4909)1/3 = 4.1510-4 M

Finally

S = 4.1510-4/2 = 2.110-4

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

[H3O+], M Solubility, M

S = [Ba2+]

[ H 3O ][SO 24 ]
1.0210-2 (2)
[ HSO 4 ]

## Substituting (6) into (1) gives

246.1[SO42-]2 = 1.110-10

[SO42-] = 6.710-7 M

## From (6) [Ba2+] = 1.610-4 M = S

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

[H3O+] S, mol/L

## (d) 0.200 4.7610-5

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

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

[ H 3O ][ HS ]
K2 = 1.310-14 (2)
H 2S

[ H 3O ]2 [S 2 ]
K1K2 = 1.2510-21 (3)
H 2S
From mass-balance consideration

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

[ H 3O ][S2 ] [ H 3O ]2 [S2 ] [ H O ] [ H 3 O ]2
[M2+] = [S2-] + [S2 ]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
K 2 K K
1 2

[ H 3O ] [ H 3O ]2
[M2+] = K sp 1 (6)
1.3 10
14
1.25 10 21

(a) Substituting Ksp = 810-37 and [H3O+] = 2.010-1 into (6) gives

[M2+] = solubility =

8 10 37 1
0.20

0.202
1.3 10
14
1.25 10 21

= 5.1 10 9 M

(b) Substituting Ksp = 810-37 and [H3O+] = 2.010-4 into (6) gives

solubility = 5.1 10 12 M

11-9 (a) Substituting Ksp = 110-27 and [H3O+] = 2.010-1 into (6) gives

solubility = 2 10 4 M

(b) Substituting Ksp = 110-27 and [H3O+] = 2.010-4 into (6) gives

solubility = 210-7 M

11-10 (a) Substituting Ksp = 310-14 and [H3O+] = 2.010-5 into (6) gives

solubility = 0.1 M

(b) Substituting Ksp = 310-14 and [H3O+] = 2.010-7 into (6) gives

solubility = 110-3 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

## 11-11 PbCO3 Pb2+ + CO32- Ksp = [Pb2+][CO32-] = 7.410-14

[ H 3O ][ HCO -3 ]
H2CO3 + H2O H3O+ + HCO3- K1 = 4.4510-7
[ H 2 CO 3 ]

[ H 3O ][CO 32- ]
HCO3- + H2O H3O+ + CO32- K2 =
4.6910-11
[ HCO 3 ]

[H3O+] = 110-7

## 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

## 11-12 Ag2SO3 2Ag+ + SO32- Ksp = [Ag+]2[SO32-] = 1.510-14 (1)

[ H 3O ][ HSO -3 ]
H2SO3 + H2O H3O+ + HSO3- K1 = 1.2310-2 (2)
[ H 2SO 3 ]

- + 2- [ H 3O ][SO 32- ]
HSO3 + H2O H3O + SO3 K2 =
6.610-8 (3)
[ HSO3 ]

[ H 3O ]2 [SO 32- ]
H2SO3 + 2H2O 2H3O+ + SO32- K1K2 = 8.110-10 (4)
[ H 2SO 3 ]

## [H3O+] = 110-8 (6)

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

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

+
[Ag ] = [SO3 ] +2- 1 10 [SO
8 2-
3 ]
+
1 10 [SO
8 2 2-
3 ]
6.6 10 -8
8.1 10 -10

+

2-
[Ag ] = [SO3 ] 1
1 10 8

1 10 8
2

6.6 10 -8 8.1 10 10

## Substituting (1) into this expression gives

1 1 10 1 10
K sp 8 8 2
[Ag+] =

Ag 6.6 10
2 -8
8.1 10 10

[Ag+]3 = 21.510-14 1
1 10 8

1 108 2
6.6 10 -8 8.1 10 10

[Ag+] = 4.210-5

Solubility = 2.110-5 M

## To initiate precipitation of Ba(IO3)2

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

## [SCN-]/[I-] = 1.110-9/(8.310-14) = 1.3104

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

## SrSO4 begins to precipitate before the Ba2+ concentration is reduced to 1.010-6 M.

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

## [SO42-] = 1.610-5/(0.020)2 = 0.040 M

Ag2SO4 does not precipitate before the Ba2+ concentration is reduced to 1.010-6 M.

## Be precipitation complete when [OH-] = (7.010-22/1.010-6)1/2 = 2.610-8 M

Hf(OH)4 does not precipitate before the Be2+ concentration is reduced to 1.010-6 M.

## 11-17 AgBr Ag+ + Br- 5.010-13 = [Ag+][Br-] (1)

[Ag (CN) 2 ]
Ag+ + 2CN- Ag(CN)2- 1.31021 = (2)
[Ag ][CN ]2

## 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

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

0.0500
[CN-] = = 2.010-6 ( 210-6 << 0.100)
11

1 10 1.3 10 21
Thus, the two assumptions are valid and

## 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-] = 1.910-7 (1)

[CuCl-2 ]
Cu+ + 2Cl- CuCl2- 2 = - 2
= 7.9104 (2)
[Cu ][Cl ]

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

[CuCl -2 ]
-
= 1.910-77.9104 = 1.510-2 (3)
[Cl ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

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

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

1.9 107
[Cl-] = [Na+] + -
- 1.510-2[Cl-]
[Cl ]

## 0 = 1.015[Cl-]2 - [Na+][Cl-] - 1.910-7 (5)

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

following [Cl-]

## (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

+ 1.9 107
-
S = [Cu ] + [CuCl2 ] =
+ 1.510-2[Cl-]
[Cl ]

## (b) 3.010-3 M (d) 1.210-4 M

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11

## [Ca 2 ][SO 24- ]

CaSO4(aq) Ca2+ + SO42- Kd = = 5.210-3 (2)
[CaSO 4 ( aq)]

## [CaSO4(aq)] = Ksp/Kd = (2.610-5)/(5.210-3) = 5.010-3

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

## %CaSO4(aq) = (5.010-3/1.0110-2)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 5.010-3 and the mass balance gives

## [SO42-] = 0.0121 and [Ca2+] = 2.1410-3

Fundamentals of Analytical Chemistry: 8th ed. Chapter 11