Chapter 11
Chapter 11
[ H 3O ]2 [S2 ]
K1 K 2
[ H 2S]
[ H 2S] K
[S2 ] K1 K 2 or [S2 ]
[ H 3 O ]2 [ H 3 O ]2
112 The simplifications in equilibrium calculations involve assuming that the concentrations
113 A chargebalance equation is derived by relating the concentration of cations and anions
such that
For a doubly charged ion, such as Ba2+, the concentration electrons for each mole is twice
Thus, the molar concentration of all multiply charged species is always multiplied by the
0.100 = [Na+]
[Na+] = 0.25
[ 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 ]

[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 = 3.29107[C2O42]
5.60 10 2
[Ag+] = 2.037[C2O42] or
[C2O42] = 0.4909[Ag+]
Finally
S = 4.15104/2 = 2.1104
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 ]
1.02102 (2)
[ HSO 4 ]
246.1[SO42]2 = 1.11010
[SO42] = 6.7107 M
[H3O+] S, mol/L
118 The following derivation applies to this and the following two problems.
[ H 3O ][ HS ]
K2 = 1.31014 (2)
H 2S
[ H 3O ]2 [S 2 ]
K1K2 = 1.251021 (3)
H 2S
From massbalance consideration
[ 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
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 = 81037 and [H3O+] = 2.0101 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 = 81037 and [H3O+] = 2.0104 into (6) gives
solubility = 5.1 10 12 M
119 (a) Substituting Ksp = 11027 and [H3O+] = 2.0101 into (6) gives
solubility = 2 10 4 M
(b) Substituting Ksp = 11027 and [H3O+] = 2.0104 into (6) gives
solubility = 2107 M
1110 (a) Substituting Ksp = 31014 and [H3O+] = 2.0105 into (6) gives
solubility = 0.1 M
(b) Substituting Ksp = 31014 and [H3O+] = 2.0107 into (6) gives
solubility = 1103 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11
[ H 3O ][ HCO 3 ]
H2CO3 + H2O H3O+ + HCO3 K1 = 4.45107
[ H 2 CO 3 ]
[ H 3O ][CO 32 ]
HCO3 + H2O H3O+ + CO32 K2 =
4.691011
[ HCO 3 ]
[H3O+] = 1107
[ 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
[ H 3O ][ HSO 3 ]
H2SO3 + H2O H3O+ + HSO3 K1 = 1.23102 (2)
[ H 2SO 3 ]
 + 2 [ H 3O ][SO 32 ]
HSO3 + H2O H3O + SO3 K2 =
6.6108 (3)
[ HSO3 ]
[ H 3O ]2 [SO 32 ]
H2SO3 + 2H2O 2H3O+ + SO32 K1K2 = 8.11010 (4)
[ H 2SO 3 ]
+
[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
1 1 10 1 10
K sp 8 8 2
[Ag+] =
Ag 6.6 10
2 8
8.1 10 10
[Ag+]3 = 21.51014 1
1 10 8
1 108 2
6.6 10 8 8.1 10 10
[Ag+] = 4.2105
Solubility = 2.1105 M
Note that this ratio is independent of [Ag+] as long as some AgSCN(s) is present.
Ag2SO4 does not precipitate before the Ba2+ concentration is reduced to 1.0106 M.
Hf(OH)4 does not precipitate before the Be2+ concentration is reduced to 1.0106 M.
[Ag (CN) 2 ]
Ag+ + 2CN Ag(CN)2 1.31021 = (2)
[Ag ][CN ]2
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
0.0500
[CN] = = 2.0106 ( 2106 << 0.100)
11
1 10 1.3 10 21
Thus, the two assumptions are valid and
= 1.877 g
[CuCl2 ]
Cu+ + 2Cl CuCl2 2 =  2
= 7.9104 (2)
[Cu ][Cl ]
[CuCl 2 ]

= 1.91077.9104 = 1.5102 (3)
[Cl ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 11
From a charge balance consideration, we can write (if we assume [H3O+] = [OH])
1.9 107
[Cl] = [Na+] + 
 1.5102[Cl]
[Cl ]
By using [Na+] = the NaCl analytical concentration, (5) can be solved to give the
following [Cl]
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]
The solubility of CuCl can be obtained from the calculated [Cl] and the expression
+ 1.9 107

S = [Cu ] + [CuCl2 ] =
+ 1.5102[Cl]
[Cl ]
Note that this is the equilibrium constant expression for (3) and indicates that the
(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 5.0103 and the mass balance gives