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Chapter 16 Acid Base Equilibria and Solubility Equilibria
Chapter 16 Acid Base Equilibria and Solubility Equilibria
Solubility Equilibria
Chapter 16
1
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The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.
Ka [HA]
[H ] =
+
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-] [conjugate base]
- pH = pKa + log
-log [H ] = -log Ka + log
+ [A ] [acid]
[HA]
-
pH = pKa + log [A ] pKa = -log Ka
[HA]
3
Example 16.1
4
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
5
[CH COO ] at equilibrium.
-
Example 16.1
Solution
(a) In this case, the changes are
[H + ][CH 3COO - ]
Ka =
[CH 3COOH]
2
x
1.8 × 10-5 =
0.20-x
6
Example 16.1
2 2
x x
1.8 × 10-5 =
0.20-x 0.20
or
x = [H+] = 1.9 x 10-3 M
Thus,
7
Example 16.1
or
x = [H+] = 1.2 x 10-5 M
Thus,
pH = -log [H+]
= -log (1.2 x 10-5 ) = 4.92 9
Example 16.1
Check
Comparing the results in (a) and (b), we see that when the
common ion (CH3COO-) is present, according to Le Châtelier’s
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
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!
(a) KH2PO4/H3PO4
(b) NaClO4/HClO4
12
Example 16.2
Strategy
13
Example 16.2
(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:
[H + ][CH 3COO- ]
Ka =
[CH 3COOH]
(x)(1.0+x)
1.8 × 10-5 =
(1.0-x)
17
Example 16.3
-5 (x)(1.0+x) x(1.0)
1.8 × 10 =
(1.0-x) 1.0
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) → H+(aq) + Cl-(aq)
Initial (mol): 0.10 0 0
Change (mol): -0.10 +0.10 +0.10
Final (mol): 0 0.10 0.10
20
Example 16.3
[H + ][CH 3COO - ]
Ka =
[CH 3COOH]
-5 (x)(0.90+x)
1.8 × 10 =
(1.1-x )
21
Example 16.3
Assuming 0.90 + x ≈ 0.90 and 1.1 - x ≈ 1.1, we obtain
-5(x)(0.90+x) x(0.90)
1.8 × 10 =
(1.1-x) 1.1
or
Thus,
pH = -log (2.2 x 10-5 ) = 4.66
23
Example 16.4
24
Example 16.4
Strategy
or
[conjugate base]
1
acid
25
Example 16.4
Solution
26
Example 16.4
[conjugate base]
pH = pK a + log
[acid]
[HPO2- 4 ]
7.40 = 7.21 + log
[H 2 PO -4 ]
[HPO 2-4 ]
log -
= 0.19
[H 2 PO 4 ]
27
Example 16.4
30
monitor pH
Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)
31
Chemistry In Action: Maintaining the pH of Blood
32
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)
33
Example 16.5
34
Example 16.5
Strategy
37
Example 16.5
To calculate the pH of the solution, we write
[H + ][CH3COO - ]
Ka =
[CH3COOH]
[CH 3COOH]K a
[H + ] =
[CH 3COO - ]
(1.50 × 10-3 )(1.8 × 10-5 ) -5
= -3
= 2.7 × 10 M
1.00 × 10
Therefore,
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 × × = 2.50 × 10 -3 mol
1 L NaOH soln 1000 mL
39
Example 16.5
40
Example 16.5
[CH 3COOH][OH - ] x2
K b = 5.6 1010 = -
=
[CH3COO ] 0.0500 - x
x = [OH - ] = 5.3 × 10-6 M , pH = 8.72
41
Example 16.5
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
pOH = -log[OH - ] = -log0.0167 = 1.78
pH = 14.00-1.78 = 12.22
43
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4+ (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)
44
Example 16.6
45
Example 16.6
Strategy
The reaction between NH3 and HCl is
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 × × = 2.50 × 10-3 mol
1 L NH3 1000 mL
47
Example 16.6
48
Example 16.6
+
Step 1: We represent the hydrolysis of the cation NH 4 , and
let x be the equilibrium concentration of NH3 and H+
ions in mol/L:
49
Example 16.6
Step 2: From Table 15.4 we obtain the Ka for NH +4 :
[NH3 ][H+ ]
Ka =
[NH+4 ]
-10 x2
5.6 × 10 =
0.0500 - x
Applying the approximation 0.0500 - x ≈ 0.0500, we get
-10 x2 x2
5.6 × 10 =
0.0500 - x 0.0500
x = 5.3 × 10-6 M
Check
51
Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
-
10 Color of acid (HIn) predominates
[In ]
[HIn]
-
10 Color of conjugate base (In -
) predominates
[In ]
52
Solutions of Red Cabbage Extract
pH
53
The titration curve of a strong acid with a strong base.
54
Example 16.7
Which indicator or indicators listed in Table 16.1 would you use
for the acid-base titrations shown in
55
Example 16.7
56
Example 16.7
57
Example 16.7
Strategy
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
62
Example 16.8
63
Example 16.8
Strategy
64
Example 16.8
2
CaSO4(s) Ca2+(aq) + SO4 (aq)
Initial (M): 0 0
Change (M): -s +s +s
Equilibrium (M): s s
65
Example 16.8
66
Example 16.8
= 2.4 x 10-5
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
69
Example 16.9
Ksp = [Cu2+][OH-]2
= (s)(2s)2 = 4s3
70
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
-20
2.2 × 10
s3 = = 5.5 × 10-21
4
s = 1.8 × 10-7 M
Hence
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 × × = 8.0 × 10-4 mol Ba 2+
1 L soln 1000 mL
-4
8.0 × 10 mol 1000 mL
[Ba 2+ ] = ×
800 mL 1 L soln
= 1.0 × 10-3 M
76
Example 16.10
2
The number of moles of SO4 in the original 600 mL solution is
77
Example 16.10
Now we must compare Q and Ksp. From Table 16.2,
2
BaSO4(s) Ba (aq) +
2+ SO 4 (aq) Ksp = 1.1 x 10-10
As for Q,
2
Q = [Ba ]0[
2+ SO 4 ] = (1.0 x 10-3)(6.0 x 10-3)
0
= 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
SO24
[Ba2+][ ] = 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
K sp 7.7 × 10 -13
[Ag + ] = -
=
[Br ] 0.020
= 3.9 × 10-11 M
so that
K sp 1.6 × 10 -10
[Ag + ] = - =
[Cl ] 0.020
= 8.0 × 10-9 M
83
Example 16.12
84
Example 16.12
Strategy
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.
86
Example 16.12
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
Step 4: At equilibrium
88
Example 16.12
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 Châtelier’s principle. Adding Ag+ ions shifts
the equilibrium to the left, thus decreasing the solubility of AgCl.
90
pH and Solubility
• The presence of a common ion decreases the solubility.
• Insoluble bases dissolve in acidic solutions
• Insoluble acids dissolve in basic solutions
remove
add
Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)
(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
The sulfide ion is the conjugate base of the weak acid HS-.
Therefore, the S2- ion reacts with the H+ ion as follows:
95
Example 16.13
(c) The solubility equilibrium for PbSO4 is
2
PbSO4(s) Pb (aq) +
2+ SO 4 (aq)
SO24
This reaction removes the ions from solution. According
to Le Châtelier’s principle, the equilibrium
2 will shift to the
SO4
right to replace some of the ions that were removed,
thereby increasing the solubility of PbSO4. 96
Example 16.14
97
Example 16.14
Strategy
98
Example 16.14
Solution
99
Example 16.14
-14
1.6 × 10
[OH - ]2 = = 5.3 × 10-12
0.0030
[OH - ] = 2.3 × 10-6 M
100
Example 16.14
101
Example 16.14
[NH +4 ][OH - ]
Kb =
[NH 3 ]
1.8 × 10 -5
=
2.3 × 10-6 2.3 × 10-6
(x - 2.3 × 10-6 )
x = 2.6 x 10-6 M
102
Complex Ion Equilibria and Solubility
A complex ion is an ion containing a central metal cation
bonded to one or more molecules or ions.
Co2+ (aq) + 4Cl- (aq) CoCl42-(aq)
stability of
Kf
HCl complex
103
104
Example 16.15
105
Example 16.15
Strategy The addition of CuSO4 to the NH3 solution results in
complex ion formation
Cu (aq) + 4NH3(aq)
2+ Cu(NH 3 ) 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 2that essentially all
Cu(NH 3 ) 4
the dissolved Cu2+ ions end up as ions. How many
moles of NH3 will 2react
with 0.20 mole of Cu2+? How many
Cu(NH 3 ) 4
moles of 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
2
(1.20 - 0.80) mol/L soln or
Cu(NH 3 ) 4
0.40 M, and that of is 0.20 mol/L soln or 0.20 M, the
same as the initial concentration2of Cu2+. [There is a 1:1 2 mole
Cu(NH 3 ) 4
ratio between Cu2+ and .] Because Cu(NH 3 ) 4
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
13 0.20
5.0 × 10 =
x(0.40) 4
107
Example 16.15
Check
108
Example 16.16
109
Example 16.16
Strategy
AgCl is only slightly soluble in water
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
complex ion Ag(NH )
3 2 .
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:
The formation constant for Ag(NH3 )2 is quite large, so most of
the silver ions exist in the complexed form. In the absence of
ammonia we have, at equilibrium, [Ag+] = [Cl-]. As a result of
complex ion formation, however, we can write[ Ag(NH )
3 2] =
[Cl-].
113
Example 16.16
Step 3: (s )(s)
K=
(1.0 - 2s ) 2
3 s2
2.4 × 10 =
(1.0 - 2s) 2
s
0.049 =
1.0 - 2s
s = 0.045 Μ
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
Chemistry In Action: How an Eggshell is Formed
electron micrograph
116
Effect of Complexation on Solubility
AgNO
Add3 +
NHNaCl
3
Ag(NH
AgCl 3)2+ 117
118
Qualitative
Analysis of
Cations
119
Flame Test for Cations
120