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Solubility Equilibria
Chapter 16
1
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CH3COONa (s)
CH3COOH (aq)
common
ion
2
HA (aq)
H+ (aq) + A- (aq)
[H+]
Ka [HA]
=
[A-]
[HA]
[A-]
-]
[A
-log [H+] = -log Ka + log
[HA]
[A-]
pH = pKa + log
[HA]
[H+][A-]
Ka =
[HA]
Henderson-Hasselbalch
equation
[conjugate base]
pH = pKa + log
[acid]
pKa = -log Ka
3
Example 16.1
Example 16.1
Strategy
(a) We calculate [H+] and hence the pH of the solution by
following the procedure in Example 15.8.
(b) CH3COOH is a weak acid (CH3COOH
CH3COO- + H+),
and CH3COONa is a soluble salt that is completely
dissociated in solution (CH3COONa Na+ + CH3COO-).
The common ion here is the acetate ion, CH3COO-. At
equilibrium, the major species in solution are CH3COOH,
CH3COO-, Na+, H+, and H2O. The Na+ ion has no acid or
base properties and we ignore the ionization of water.
Because Ka is an equilibrium constant, its value is the same
whether we have just the acid or a mixture of the acid and
its salt in solution. Therefore, we can calculate [H+] at
equilibrium and hence pH if we know both [CH3COOH] and
[CH3COO-] at equilibrium.
5
Example 16.1
Solution
(a) In this case, the changes are
CH3COOH(aq)
Initial (M):
Change (M):
Equilibrium (M):
H+(aq) + CH3COO-(aq)
0.20
-x
+x
+x
0.20-x
[H + ][CH3COO- ]
Ka =
[CH3COOH]
2
x
1.8 10-5 =
0.20-x
6
Example 16.1
Assuming 0.20 - x 0.20, we obtain
2
2
x
x
1.8 10-5 =
0.20-x
0.20
or
x = [H+] = 1.9 x 10-3 M
Thus,
pH= -log (1.9 x 10-3 ) = 2.72
Example 16.1
Sodium acetate is a strong electrolyte, so it dissociates
completely in solution:
CH3COONa(aq) Na+(aq) + CH3COO-(aq)
0.30 M
0.30 M
The initial concentrations, changes, and final concentrations of
the species involved in the equilibrium are
CH3COOH(aq)
Initial (M):
Change (M):
Equilibrium (M):
H+(aq) + CH3COO-(aq)
0.20
-x
0
+x
0.30
+x
0.20-x
0.30+x
8
Example 16.1
From Equation (16.1),
[H + ][CH 3COO- ]
Ka =
[CH3COOH]
(x)(0.30+x)
1.8 10 =
0.20-x
-5
or
(x)(0.30+x)
(x)(0.30)
0.20-x
0.20
Example 16.1
Check
Comparing the results in (a) and (b), we see that when the
common ion (CH3COO-) is present, according to Le Chteliers
principle, the equilibrium shifts from right to left. This action
decreases the extent of ionization of the weak acid.
Consequently, fewer H+ ions are produced in (b) and the pH of
the solution is higher than that in (a). As always, you should
check the validity of the assumptions.
10
CH3COOH (aq)
CH3COO- (aq) + H2O (l)
11
Example 16.2
Which of the following solutions can be classified as buffer
systems?
(a) KH2PO4/H3PO4
(b) NaClO4/HClO4
(c) C5H5N/C5H5NHCl (C5H5N is pyridine; its Kb is given in
Table 15.4)
Explain your answer.
12
Example 16.2
Strategy
What constitutes a buffer system? Which of the preceding
solutions contains a weak acid and its salt (containing the weak
conjugate base)? Which of the preceding solutions contains a
weak base and its salt (containing the weak conjugate acid)?
Why is the conjugate base of a strong acid not able to
neutralize an added acid?
13
Example 16.2
Solution The criteria for a buffer system is that we must have a
weak acid and its salt (containing the weak conjugate base) or
a weak base and its salt (containing the weak conjugate acid).
(a) H3PO4 is a weak acid, and its conjugate base, H2PO-4 ,is a
weak base (see Table 15.5). Therefore, this is a buffer
system.
(b) Because HClO4 is a strong acid, its conjugate base, ClO4 , is
an extremely weak base. This means that the ClO-4 ion will
not combine with a H+ ion in solution to form HClO4. Thus,
the system cannot act as a buffer system.
(c) As Table 15.4 shows, C5H5N is a weak base and its
conjugate acid, C5H5N+H (the cation of the salt C5H5NHCl),
is a weak acid. Therefore, this is a buffer system.
14
Example 16.3
(b) What is the pH of the buffer system after the addition of 0.10
mole of gaseous HCl to 1.0 L of the solution? Assume that
the volume of the solution does not change when the HCl is
added.
15
Example 16.3
Strategy
(a) The pH of the buffer system before the addition of HCl can
be calculated with the procedure described in Example 16.1,
because it is similar to the common ion problem. The Ka of
CH3COOH is 1.8 x 10-5 (see Table 15.3).
(b) It is helpful to make a sketch of the changes that occur in
this case.
16
Example 16.3
Solution (a) We summarize the concentrations of the species
at equilibrium as follows:
CH3COOH(aq)
Initial (M):
Change (M):
Equilibrium (M):
H+(aq) + CH3COO-(aq)
1.0
-x
1.0-x
0
+x
x
1.0
+x
1.0+x
[H + ][CH 3COO- ]
Ka =
[CH 3COOH]
1.8 10-5 =
(x)(1.0+x)
(1.0-x)
17
Example 16.3
(x)(1.0+x)
x(1.0)
1.8 10 =
(1.0-x)
1.0
-5
or
x = [H+] = 1.8 x 10-5 M
Thus,
pH = -log (1.8 x 10-5 ) = 4.74
18
Example 16.3
(b) When HCl is added to the solution, the initial changes are
HCl(aq)
Initial (mol):
Change (mol):
Final (mol):
0.10
-0.10
0
H+(aq) +
0
+0.10
0.10
Cl-(aq)
0
+0.10
0.10
Example 16.3
The neutralization reaction is summarized next:
CH3COO-(aq)
Initial (mol):
Change (mol):
Final (mol):
1.0
-0.10
0.90
+ H+(aq) CH3COOH(aq)
0.10
-0.10
0
1.0
+0.10
1.1
20
Example 16.3
CH3COOH(aq)
Initial (M):
Change (M):
Equilibrium (M):
H+(aq) + CH3COO-(aq)
1.1
-x
1.1-x
0
+x
x
0.90
+x
0.90+x
[H + ][CH 3COO- ]
Ka =
[CH 3COOH]
(x)(0.90+x)
1.8 10 =
(1.1-x)
-5
21
Example 16.3
Assuming 0.90 + x 0.90 and 1.1 - x 1.1, we obtain
(x)(0.90+x)
x(0.90)
1.8 10 =
(1.1-x)
1.1
-5
or
HCl
HCl + CH3COO-
H+ + ClCH3COOH + Cl-
23
Example 16.4
24
Example 16.4
Strategy
[conjugate base]
log
0
[acid]
or
[conjugate base]
1
acid
25
Example 16.4
Solution
+
3HPO 2(
aq
)
H
(
aq
)
+
PO
4
4 (aq )
26
Example 16.4
The most suitable of the three buffer systems is HPO2/H
PO
4
2
4,
because the pKa of the acid H2PO-4 is closest to the desired pH.
From the Henderson-Hasselbalch equation we write
[conjugate base]
pH = pK a + log
[acid]
[HPO24 ]
7.40 = 7.21 + log
[H 2 PO -4 ]
[HPO 24 ]
log
= 0.19
[H 2 PO 4 ]
27
Example 16.4
Taking the antilog, we obtain
[HPO 20.19
4 ]
=
10
= 1.5
[H 2 PO 4 ]
Thus, one way to prepare a phosphate buffer with a pH of 7.40
is to dissolve disodium hydrogen phosphate (Na2HPO4) and
sodium dihydrogen phosphate (NaH2PO4) in a mole ratio of
1.5:1.0 in water. For example, we could dissolve 1.5 moles of
Na2HPO4 and 1.0 mole of NaH2PO4 in enough water to make
up a 1-L solution.
28
Titrations (Review)
In a titration, a solution of accurately known concentration is
gradually added to another solution of unknown concentration
until the chemical reaction between the two solutions is
complete.
Equivalence point the point at which the reaction is complete
29
monitor pH
30
31
32
33
Example 16.5
Calculate the pH in the titration of 25.0 mL of 0.100 M acetic
acid by sodium hydroxide after the addition to the acid solution
of
(a) 10.0 mL of 0.100 M NaOH
(b) 25.0 mL of 0.100 M NaOH
34
Example 16.5
Strategy
CH3COONa(aq) + H2O(l)
Example 16.5
Solution
(a) The number of moles of NaOH in 10.0 mL is
Example 16.5
The changes in number of moles are summarized next:
CH3COONa(aq) + H2O(l)
CH3COOH (aq)
+ NaOH (aq)
Initial (mol):
2.50 x 10-3
1.00 x 10-3
Change (mol):
-1.00 x 10-3
-1.00 x 10-3
+1.00 x 10-3
Final (mol):
1.50 x 10-3
1.00 x 10-3
37
Example 16.5
To calculate the pH of the solution, we write
[H + ][CH3COO- ]
Ka =
[CH3COOH]
[H + ] =
[CH 3COOH]K a
[CH 3COO- ]
10
M
-3
1.00 10
Therefore,
pH = -log (2.7 x 10-5) = 4.57
38
Example 16.5
(b) These quantities (that is, 25.0 mL of 0.100 M NaOH reacting
with 25.0 mL of 0.100 M CH3COOH) correspond to the
equivalence point. The number of moles of NaOH in 25.0
mL of the solution is
0.100 mol NaOH
1L
25.0 mL
CH3COOH (aq)
+ NaOH (aq)
Initial (mol):
2.50 x 10-3
2.50 x 10-3
Change (mol):
-2.50 x 10-3
-2.50 x 10-3
+2.50 x 10-3
2.50 x 10-3
Final (mol):
+ H2O(l)
39
Example 16.5
At the equivalence point, the concentrations of both the acid
and the base are zero. The total volume is (25.0 + 25.0) mL or
50.0 mL, so the concentration of the salt is
50.0 mL
1L
= 0.0500 mol/L = 0.0500 M
40
Example 16.5
K b = 5.6 1010
[CH 3COOH][OH - ]
x2
=
=
0.0500 - x
[CH3COO ]
41
Example 16.5
(c) After the addition of 35.0 mL of NaOH, the solution is well
past the equivalence point. The number of moles of
NaOH originally present is
35.0 mL
CH3COOH (aq)
+ NaOH (aq)
Initial (mol):
2.50 x 10-3
3.50 x 10-3
Change (mol):
-2.50 x 10-3
-2.50 x 10-3
+2.50 x 10-3
1.00 x 10-3
2.50 x 10-3
Final (mol):
42
Example 16.5
At this stage we have two species in solution that are
responsible for making the solution basic: OH- and CH3COO(from CH3COONa). However, because OH- is a much
stronger base than CH3COO-, we can safely neglect the
hydrolysis of the CH3COO- ions and calculate the pH of the
solution using only the concentration of the OH- ions. The
total volume of the combined solutions is (25.0 + 35.0) mL or
60.0 mL, so we calculate OH- concentration as follows:
-3
1.00
10
mol 1000 mL
[OH ] =
60.0 mL
1L
= 0.0167 mol/L = 0.0167 M
NH4Cl (aq)
NH4+ (aq)
44
Example 16.6
45
Example 16.6
Strategy
The reaction between NH3 and HCl is
NH3(aq) + HCl(aq)
NH4Cl(aq)
46
Example 16.6
Solution The number of moles of NH3 in 25.0 mL of 0.100 M
solution is
0.100 mol NH3
1L
25.0 mL
Initial (mol):
Change (mol):
Final (mol):
NH3(aq) +
HCl(aq)
2.50 x 10-3
-2.50 x 10-3
0
2.50 x 10-3
-2.50 x 10-3
0
NH4Cl(aq)
0
+ 2.50 x 10-3
2.50 x 10-3
47
Example 16.6
At the equivalence point, the concentrations of both the acid
and the base are zero. The total volume is (25.0 + 25.0) mL,
or 50.0 mL, so the concentration of the salt is
2.50 10 -3 mol 1000 mL
[NH 4 Cl] =
50.0 mL
1L
= 0.0500 mol/L = 0.0500 M
48
Example 16.6
+
NH+4 (aq)
Initial (M):
Change (M):
Equilibrium (M):
0.0500
-x
(0.0500-x)
NH3(aq)
0.000
+x
x
H+(aq)
0.000
+x
x
49
Example 16.6
Step 2: From Table 15.4 we obtain the Ka for NH+4 :
[NH3 ][H+ ]
Ka =
[NH+4 ]
5.6 10
-10
x2
=
0.0500 - x
0.0500 - x 0.0500
x = 5.3 10-6 M
-10
50
Example 16.6
Check
Note that the pH of the solution is acidic. This is what we would
expect from the hydrolysis of the ammonium ion.
51
Acid-Base Indicators
HIn (aq)
H+ (aq) + In- (aq)
[HIn]
10 Color of acid (HIn) predominates
[In ]
[HIn]
-) predominates
Color
of
conjugate
base
(In
10
[In-]
52
pH
53
54
Example 16.7
Which indicator or indicators listed in Table 16.1 would you use
for the acid-base titrations shown in
(a) Figure 16.4?
55
Example 16.7
(b) Figure 16.5?
56
Example 16.7
(c) Figure 16.6?
57
Example 16.7
Strategy
The choice of an indicator for a particular titration is based on
the fact that its pH range for color change must overlap the
steep portion of the titration curve. Otherwise we cannot use
the color change to locate the equivalence point.
58
Example 16.7
Solution
(a) Near the equivalence point, the pH of the solution changes
abruptly from 4 to 10. Therefore, all the indicators except
thymol blue, bromophenol blue, and methyl orange are
suitable for use in the titration.
(b) Here the steep portion covers the pH range between 7 and
10; therefore, the suitable indicators are cresol red and
phenolphthalein.
(c) Here the steep portion of the pH curve covers the pH range
between 3 and 7; therefore, the suitable indicators are
bromophenol blue, methyl orange, methyl red, and
chlorophenol blue.
59
Solubility Equilibria
AgCl (s)
Ksp = [Ag+][Cl-]
MgF2 (s)
Ag2CO3 (s)
Ca3(PO4)2 (s)
Ksp = [Mg2+][F-]2
Ksp = [Ag+]2[CO32-]
Ksp = [Ca2+]3[PO43-]2
Unsaturated solution
Q = Ksp
Saturated solution
Q > Ksp
Supersaturated solution
No precipitate
61
62
Example 16.8
63
Example 16.8
Strategy
We are given the solubility of CaSO4 and asked to calculate its
Ksp. The sequence of conversion steps, according to Figure
16.9(a), is
solubility of
CaSO4 in g/L
molar solubility
of CaSO4
[Ca2+] and
[ SO24 ]
Ksp of
CaSO4
64
Example 16.8
Solution Consider the dissociation of CaSO4 in water. Let s
be the molar solubility (in mol/L) of CaSO4.
CaSO4(s)
Initial (M):
Change (M):
Equilibrium (M):
2
Ca2+(aq) + SO4 (aq)
-s
0
+s
s
0
+s
s
Example 16.8
First, we calculate the number of moles of CaSO4 dissolved in
1 L of solution:
0.67 g CaSO4
1 mol CaSO4
66
Example 16.8
67
Example 16.9
Using the data in Table 16.2, calculate the solubility of
copper(II) hydroxide, Cu(OH)2, in g/L.
68
Example 16.9
Strategy
We are given the Ksp of Cu(OH)2 and asked to calculate its
solubility in g/L. The sequence of conversion steps, according
to Figure 16.9(b), is
Ksp of
Cu(OH)2
[Cu2+] and
[OH-]
molar solubilty
of Cu(OH)2
solubility of
Cu(OH)2 in g/L
69
Example 16.9
Consider the dissociation of Cu(OH)2 in water:
Cu(OH)2(s)
Initial (M):
Change (M):
-s
Equilibrium (M):
Cu2+(aq) + 2OH-(aq)
0
+s
0
+2s
2s
Example 16.9
From the Ksp value in Table 16.2, we solve for the molar
solubility of Cu(OH)2 as follows:
2.2 10-20 = 4s 3
Hence
-20
2.2
10
s3 =
= 5.5 10-21
4
s = 1.8 10-7 M
1 L soln
1 mol Cu(OH)2
= 1.8 10-5 g / L
71
72
Example 16.10
73
Example 16.10
Strategy
74
Example 16.10
75
Example 16.10
Solution
The number of moles of Ba2+ present in the original 200 mL of
solution is
0.0040 mol Ba 2+
1L
200 mL
10
mol 1000 mL
[Ba 2+ ] =
800 mL
1 L soln
= 1.0 10-3 M
76
Example 16.10
The number of moles of SO24 in the original 600 mL solution is
0.0080 mol SO24
1L
600 mL
-3
4.8
10
mol 1000 mL
2
[SO 4 ] =
800 mL
1 L soln
= 6.0 10-3 M
77
Example 16.10
Now we must compare Q and Ksp. From Table 16.2,
BaSO4(s)
As for Q,
Q = [Ba2+]0[ SO24 ]0 = (1.0 x 10-3)(6.0 x 10-3)
= 6.0 x 10-6
Therefore, Q > Ksp
The solution is supersaturated because the value of Q indicates
that the concentrations of the ions are too large. Thus, some of
the BaSO4 will precipitate out of solution until
2
[Ba2+][ SO4 ] = 1.1 x 10-10
78
Example 16.11
79
Example 16.11
Strategy
In solution, AgNO3 dissociates into Ag+ and NO3 ions. The Ag+
ions then combine with the Cl- and Br- ions to form AgCl and
AgBr precipitates. Because AgBr is less soluble (it has a
smaller Ksp than that of AgCl), it will precipitate first. Therefore,
this is a fractional precipitation problem. Knowing the
concentrations of Cl- and Br- ions, we can calculate [Ag+] from
the Ksp values. Keep in mind that Ksp refers to a
saturated solution. To initiate precipitation, [Ag+] must exceed
the concentration in the saturated solution in each case.
80
Example 16.11
Solution The solubility equilibrium for AgBr is
AgBr(s)
Ag+(aq) + Br-(aq)
Ksp = [Ag+][Br-]
10
[Ag + ] =
=
0.020
[Br ]
Ksp
= 3.9 10-11 M
Thus, [Ag+] > 3.9 x 10-11 M is required to start the precipitation
of AgBr.
81
Example 16.11
The solubility equilibrium for AgCl is
AgCl(s)
Ag+(aq) + Cl-(aq)
Ksp = [Ag+][Cl-]
so that
-10
1.6
10
[Ag + ] = - =
0.020
[Cl ]
Ksp
= 8.0 10-9 M
Therefore, [Ag+] > 8.0 x 10-9 M is needed to initiate the
precipitation of AgCl. To precipitate the Br- ions as AgBr without
precipitating the Cl- ions as AgCl, then, [Ag+] must be greater
than 3.9 x 10-11 M and lower than 8.0 x 10-9 M.
82
83
Example 16.12
84
Example 16.12
Strategy
This is a common-ion problem. The common ion here is Ag+,
which is supplied by both AgCl and AgNO3. Remember that the
presence of the common ion will affect only the solubility of
AgCl (in g/L), but not the Ksp value because it is an
equilibrium constant.
85
Example 16.12
Solution
Step 1: The relevant species in solution are Ag+ ions (from both
AgCl and AgNO3) and Cl- ions. The NO3 ions are
spectator ions.
Step 2: Because AgNO3 is a soluble strong electrolyte, it
dissociates completely:
AgNO3(s)
6.5 x 10-3 M
H2O
NO
+
3 (aq)
6.5 x 10-3 M
Ag+(aq)
86
Example 16.12
Let s be the molar solubility of AgCl in AgNO3 solution. We
summarize the changes in concentrations as follows:
AgCl(s)
Initial (M):
Change (M):
Equilibrium (M):
-s
Ag+(aq)
Cl-(aq)
6.5 x 10-3
+s
0.00
+s
Step 3:
Ksp = [Ag+][Cl-]
1.6 x 10-10 = (6.5 x 10-3 + s)(s)
87
Example 16.12
Because AgCl is quite insoluble and the presence of Ag+ ions
from AgNO3 further lowers the solubility of AgCl, s must be very
small compared with 6.5 x 10-3. Therefore, applying the
approximation 6.5 x 10-3 + s 6.5 x 10-3 , we obtain
1.6 x 10-10 = (6.5 x 10-3 )s
s = 2.5 x 10-8 M
Step 4: At equilibrium
[Ag+] = (6.5 x 10-3 + 2.5 x 10-8 ) M 6.5 x 10-3 M
[Cl+] = 2.5 x 10-8 M
88
Example 16.12
1 L soln
1 mol AgCl
= 3.6 10-6 g / L
89
Example 16.12
Check
The solubility of AgCl in pure water is 1.9 x 10-3 g/L (see the
Practice Exercise in Example 16.9). Therefore, the lower
solubility (3.6 x 10-6 g/L) in the presence of AgNO3 is
reasonable. You should also be able to predict the lower
solubility using Le Chteliers principle. Adding Ag+ ions shifts
the equilibrium to the left, thus decreasing the solubility of AgCl.
90
pH and Solubility
Mg(OH)2 (s)
Example 16.13
Which of the following compounds will be more soluble in acidic
solution than in water:
(a)CuS
(b) AgCl
(c) PbSO4
92
Example 16.13
Strategy
In each case, write the dissociation reaction of the salt into its
cation and anion. The cation will not interact with the H+ ion
because they both bear positive charges. The anion will act as
a proton acceptor only if it is the conjugate base of a
weak acid. How would the removal of the anion affect the
solubility of the salt?
93
Example 16.13
Solution
(a) The solubility equilibrium for CuS is
CuS(s)
Cu2+(aq) + S2-(aq)
The sulfide ion is the conjugate base of the weak acid HS-.
Therefore, the S2- ion reacts with the H+ ion as follows:
S2-(aq) + H+(aq)
HS-(aq)
Example 16.13
Ag+(aq) + Cl-(aq)
95
Example 16.13
(c) The solubility equilibrium for PbSO4 is
PbSO4(s)
HSO4 (aq)
2
This reaction removes the SO4 ions from solution. According
to Le Chteliers principle, the equilibrium will shift to the
2
right to replace some of the SO4 ions that were removed,
thereby increasing the solubility of PbSO4.
96
Example 16.14
97
Example 16.14
Strategy
For iron(II) hydroxide to precipitate from solution, the product
[Fe2+][OH-]2 must be greater than its Ksp. First, we calculate
[OH-] from the known [Fe2+] and the Ksp value listed in Table
16.2. This is the concentration of OH- in a saturated solution of
Fe(OH)2. Next, we calculate the concentration of NH3 that will
supply this concentration of OH- ions. Finally, any NH3
concentration greater than the calculated value will initiate the
precipitation of Fe(OH)2 because the solution will become
supersaturated.
98
Example 16.14
Solution
Example 16.14
Because FeCl2 is a strong electrolyte, [Fe2-] = 0.0030 M and
-14
1.6
10
[OH- ]2 =
= 5.3 10-12
0.0030
[OH - ] = 2.3 10-6 M
100
Example 16.14
We summarize the changes in concentrations resulting from the
ionization of NH3 as follows.
NH3 (aq)
Initial (M):
Change (M):
Equilibrium (M):
+ H2O (l)
NH4 (aq)
+ OH-(aq)
0.00
0.00
-2.3 x 10-6
+2.3 x 10-6
+2.3 x 10-6
( x -2.3 x 10-6)
2.3 x 10-6
2.3 x 10-6
101
Example 16.14
[NH +4 ][OH - ]
Kb =
[NH 3 ]
1.8 10
-5
(x - 2.3 10-6 )
102
Co(H2O)2+
6
CoCl24
HCl
Kf =
[CoCl42- ]
[Co2+][Cl-]4
Kf
stability of
complex
103
104
Example 16.15
105
Example 16.15
Strategy The addition of CuSO4 to the NH3 solution results in
complex ion formation
Cu2+(aq) + 4NH3(aq)
Cu(NH3 )24(aq)
From Table 16.4 we see that the formation constant (Kf) for this
reaction is very large; therefore, the reaction lies mostly to the
right. At equilibrium, the concentration of Cu2+ will be very small.
As a good approximation, we can assume that essentially all
the dissolved Cu2+ ions end up as Cu(NH3 )24 ions. How many
moles of NH3 will react with 0.20 mole of Cu2+? How many
moles of Cu(NH3 )24 will be produced? A very small amount of
Cu2+ will be present at equilibrium. Set up the Kf expression for
the preceding equilibrium to solve for [Cu2+ ].
106
Example 16.15
Solution The amount of NH3 consumed in forming the complex
ion is 4 x 0.20 mol, or 0.80 mol. (Note that 0.20 mol Cu2+ is
initially present in solution and four NH3 molecules are needed
to form a complex ion with one Cu2+ ion.) The concentration
of NH3 at equilibrium is therefore (1.20 - 0.80) mol/L soln or
0.40 M, and that of Cu(NH3 )24 is 0.20 mol/L soln or 0.20 M, the
same as the initial concentration of Cu2+. [There is a 1:1 mole
ratio between Cu2+ and Cu(NH3 )24.] Because Cu(NH3 )24
does dissociate to a slight extent, we call the concentration of
Cu2+ at equilibrium x and write
[Cu(NH 3 ) 24 ]
Kf =
[Cu 2+ ][NH 3 ]4
0.20
5.0 10 =
x(0.40) 4
13
107
Example 16.15
108
Example 16.16
109
Example 16.16
Strategy
AgCl is only slightly soluble in water
AgCl(s)
Ag+(aq) + Cl-(aq)
The Ag+ ions form a complex ion with NH3 (see Table 16.4)
Ag+(aq) + 2NH3(aq)
Ag(NH3 )2
110
Example 16.16
Solution
Step 1: Initially, the species in solution are Ag+ and Cl- ions and
NH3. The reaction between Ag+ and NH3 produces the
[Ag(NH3 )2 ]
7
Kf =
=
1.5
10
[Ag + ][NH3 ]2
Overall: AgCl(s) + 2NH3(aq)
Ag(NH3 )2 (aq) + Cl-(aq)
111
Example 16.16
[Ag(NH3 )2 ][Cl- ]
K =Ksp K f =
[NH3 ]2
= (1.6 10-10 )(1.5 107 )
= 2.4 10 3
112
Example 16.16
Let s be the molar solubility of AgCl (mol/L). We summarize the
changes in concentrations that result from formation of the
complex ion as follows:
AgCl(s)
Initial (M):
Change (M):
Equilibrium (M):
-s
+ 2NH3(aq)
1.0
0.0
0.0
-2s
+s
+s
(1.0 2s)
Example 16.16
Step 3:
(s)(s)
K=
(1.0 - 2s) 2
2.4 10
s2
=
(1.0 - 2s) 2
s
0.049 =
1.0 - 2s
s = 0.045
Step 4: At equilibrium, 0.045 mole of AgCl dissolves in 1 L of
1.0 M NH3 solution.
114
Example 16.16
Check
The molar solubility of AgCl in pure water is 1.3 x 10-5 M. Thus,
the formation of the complex ion Ag(NH3 )2 enhances the
solubility of AgCl (Figure 16.12).
115
CaCO3 (s)
carbonic
H2CO3 (aq)
anhydrase
H2CO3 (aq)
HCO3- (aq)
electron micrograph
116
Ag(NH
AgCl 3)2+
117
118
Qualitative
Analysis of
Cations
119
lithium
sodium
potassium
copper
120