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Topic 4 / Chapter 7
Acids
Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.
Bases
Have a bitter taste.
base
acid
conjugate
acid
conjugate
base
There must be a proton acceptor before the acid releases its proton.
16.1
16.1
16.1
16.1
Strategy
To find the conjugate base of a species, remove a proton
from the formula.
To find the conjugate acid of a species, add a proton to
the formula.
9
Solution
10
16.2
11
H2O (l)
autoionization of water
H
acid
+ H
[H
+ H
base
H2O + H2O
conjugate conjugate
acid
base
H3O+ + OH12
16.2
13
16.2
14
[H+][OH-]
Kc =
[H2O]
[H2O] = constant
Kc[H2O] = Kw = [H+][OH-]
The ion-product constant (Kw) is the product of the molar
concentrations of H+ and OH- ions at a particular temperature.
At 250C
Kw = [H+][OH-] = 1.0 x 10-14
[H+] = [OH-]
Solution Is
neutral
acidic
basic
15
Example 2
The concentration of hydronium ions in stomach acid is
0.10 M. Calculate the concentration of hydroxide ions in
stomach acid at 25C.
Strategy
Use the value of Kw to determine [OH] when [H3O+] =
0.10 M.
Setup
16
Example 2
Solution
17
pH A Measure of Acidity
pH = -log [H+]
[H+] = [OH-]
At 250C
[H+] = 1.0 x 10-7
pH = 7
acidic
pH < 7
basic
pH > 7
Solution Is
neutral
pH
[H+]
18
pH Meter
19
16.3
The pH Scale
20
16.3
The pH Scale
The pH Scale
A measured pH can be used to determine
experimentally the concentration of hydronium ion in
solution.
21
Example 3
The pH of rainwater collected in a certain region of the
northeastern United States on a particular day was 4.82.
Calculate the H+ ion concentration of the rainwater.
22
Example 3
Strategy
Here we are given the pH of a solution and asked to calculate
[H+]. Because pH is defined as pH = log [H+], we can solve for
[H+] by taking the antilog of the pH; that is, [H+] = 10pH, as
shown in Equation (16.6).
23
Example 3
Solution
From Equation (16.5)
pH = -log [H+] = 4.82
Therefore,
Example 4
In a NaOH solution [OH] is 2.9 x 104 M. Calculate the pH of
the solution.
25
Example 4
Strategy
Solving this problem takes two steps. First, we need to
calculate pOH using Equation (16.8). Next, we use Equation
(16.10) to calculate the pH of the solution.
Solution
We use Equation (16.8):
pOH = log [OH]
= log (2.9 x 104)
= 3.54
26
Example 4
Now we use Equation (16.10):
pH + pOH = 14.00
pH = 14.00 pOH
= 14.00 3.54 = 10.46
Alternatively, we can use the ion-product constant of water,
Kw = [H+][OH] to calculate [H+], and then we can calculate the
pH from the [H+]. Try it.
Check The answer shows that the solution is basic (pH > 7),
which is consistent with a NaOH solution.
27
H2O
28
H 2O
H 2O
Ba(OH)2 (s)
H 2O
29
16.4
Strong Acids
16.4
Strong Bases
Group 1A Hydroxides
Group 2A Hydroxides
31
32
The OH- ion is the strongest base that can exist in aqueous
solution.
33
34
35
Example 5
Calculate the pH of a
(a) 1.0 x 10-3 M HCl solution
(b) 0.020 M Ba(OH)2 solution
36
Example 5
Strategy
Keep in mind that HCl is a strong acid and Ba(OH)2 is a strong
base. Thus, these species are completely ionized and no HCl
or Ba(OH)2 will be left in solution.
Solution
(a)The ionization of HCl is
HCl(aq)
H+(aq) + Cl-(aq)
37
Example 5
The concentrations of all the species (HCl, H+, and Cl-) before
and after ionization can be represented as follows:
Initial (M):
Change (M):
Final (M):
H+(aq)
+ Cl-(aq)
1.0 x 10-3
-1.0 x 10-3
0.0
+1.0 x 10-3
0.0
+1.0 x 10-3
0.0
1.0 x 10-3
1.0 x 10-3
HCl(aq)
38
Example 5
(b) Ba(OH)2 is a strong base; each Ba(OH)2 unit produces two
OH- ions:
Ba(OH)2(aq)
Ba2+(aq) + 2OH-(aq)
Initial (M):
Change (M):
Final (M):
Ba2+(aq)
+ 2OH-(aq)
0.020
0.00
0.00
- 0.020
0.00
+ 0.020
0.020
+2(0.020)
0.040
Ba(OH)2(aq)
39
Example 5
Thus,
[OH-] = 0.040 M
pOH = -log 0.040 = 1.40
Therefore, from Equation (16.10),
pH = 14.00 - pOH
= 14.00 - 1.40
= 12.60
Check Note that in both (a) and (b) we have neglected the
contribution of the autoionization of water to [H+] and [OH-]
because 1.0 x 10-7 M is so small compared with 1.0 x 10-3 M
and 0.040 M.
40
Example 6
Calculate the pH of an aqueous solution at 25C that is
(a) 0.035 M in HI,
(b) 1.2 104 M in HNO3, and
(c) 6.7 105 M in HClO4.
Strategy
HI, HNO3, and HClO4 are all strong acids, so the
concentration of hydronium ion in each solution is the
same as the stated concentration of the acid.
41
Example 6
Setup
Solution
42
Example 7
Calculate the concentration of HCl in a solution at 25C
that has pH
(a) 4.95,
(b) 3.45, and
(c) 2.78.
Setup
43
Example 7
Solution
44
Example 8
Calculate the pOH of the following aqueous solutions at
25C:
(a) 0.013 M LiOH,
(b) 0.013 M Ba(OH)2,
(c) 9.2 105 M KOH.
Strategy
LiOH, Ba(OH)2, and KOH are all strong bases.
Use reaction stoichiometry to determine hydroxide ion
concentration and
to determine pOH.
45
Example 8
Setup
(a) The hydroxide ion concentration is simply equal to
the concentration of the base. Therefore, [OH] =
[LiOH] = 0.013 M.
(b) The hydroxide ion concentration is twice that of the
base:
Therefore, [OH] = 2 [Ba(OH)2] = 2(0.013 M) =
0.026 M.
(c) The hydroxide ion concentration is equal to the
concentration of the base. Therefore,
[OH] = [KOH] = 9.2 105 M.
46
Example 8
Solution
47
Example 9
Predict the direction of the following reaction in aqueous
solution:
HNO2(aq) + CN-(aq)
HCN(aq) + NO-2(aq)
48
Example 9
Strategy
The problem is to determine whether, at equilibrium, the
reaction will be shifted to the right, favoring HCN and NO-2, or to
the left, favoring HNO2 and CN-. Which of the two is a stronger
acid and hence a stronger proton donor: HNO2 or HCN? Which
of the two is a stronger base and hence a stronger proton
acceptor: CN- or NO-2 ? Remember that the stronger the acid,
the weaker its conjugate base.
49
Example 9
Solution
In Table 16.2 we see that HNO2 is a stronger acid than HCN.
Thus, CN- is a stronger base than NO-2 . The net reaction will
proceed from left to right as written because HNO2 is a better
proton donor than HCN (and CN- is a better proton acceptor
than NO-2 ).
50
HA (aq)
H+ (aq) + A- (aq)
[H+][A-]
Ka =
[HA]
Ka
weak acid
strength
51
52
Example 10
Calculate the pH of a 0.036 M nitrous acid (HNO2) solution:
HNO2(aq)
54
Example 10
Strategy Recall that a weak acid only partially ionizes in water.
We are given the initial concentration of a weak acid and asked
to calculate the pH of the solution at equilibrium. It is helpful to
make a sketch to keep track of the pertinent species.
Example 10
Solution We follow the procedure already outlined.
Step 1: The species that can affect the pH of the solution are
HNO2, H+, and the conjugate base NO-2 . We ignore
waters contribution to [H+].
Step 2: Letting x be the equilibrium concentration of H+ and
NO-2 ions in mol/L, we summarize:
Initial (M):
Change (M):
Equilibrium (M):
NO-2 (aq)
HNO2(aq)
H+(aq) +
0.036
0.00
0.00
-x
0.036 - x
+x
x
+x
x
56
Example 10
Step 3: From Table 16.3 we write
[H + ][NO-2 ]
Ka =
[HNO 2 ]
2
x
4.5 10-4 =
0.036-x
0.036-x
0.036
x 2 1.62 105
x = 4.0 103 M
57
Example 10
Step 4: At equilibrium
58
Example 11
16.12
59
Example 11
16.12
Setup
Solution
60
Example 11
16.12
Solution
61
16.5
Using pH to Determine Ka
Suppose we want to determine the Ka of a weak acid
(HA) and we know that a 0.25 M solution of the acid has
a pH of 3.47 at 25C.
[H3O+] = 103.47 = 3.39 104 M
62
Example 12
16.14
63
Example 12
16.14
Setup
Solution
64
[NH4+][OH-]
Kb =
[NH3]
Kb is the base ionization constant
Kb
weak base
strength
16.6
66
16.6
67
68
16.6
Calculating pH from Kb
Solving problems involving weak bases requires the
same approach we used for weak acids.
It is important to remember, though, that solving for x in
a typical weak base problem gives us the hydroxide ion
concentration rather than the hydronium ion
concentration.
69
Example 13
16.15
Solution
70
Example 13
16.15
Solution
71
Example 13
16.15
Solution
72
16.6
Using pH to Determine Kb
73
Example 14
16.16
74
Example 14
16.16
Setup
Solution
75
16.5
Percent Ionization
76
Example 15
16.13
77
Example 15
16.13
Solution
78
79
Example 16
Oxalic acid (H2C2O4) is a poisonous substance used chiefly as
a bleaching and cleansing agent (for example, to remove
bathtub rings). Calculate the concentrations of all the
species present at equilibrium in a 0.10 M solution.
80
Example 16
Strategy
Determining the equilibrium concentrations of the species of a
diprotic acid in aqueous solution is more involved than for a
monoprotic acid. We follow the same procedure as that used for
a monoprotic acid for each stage, as in Example 16.8. Note
that the conjugate base from the first stage of ionization
becomes the acid for the second stage ionization.
81
Example 16
Solution We proceed according to the following steps.
Step 1: The major species in solution at this stage are the
nonionized acid, H+ ions, and the conjugate base,
HC2O-4.
Initial (M):
Change (M):
Equilibrium (M):
H2C2O4(aq)
H+(aq) +
HC2O-4 (aq)
0.10
0.00
0.00
-x
0.10 - x
+x
x
+x
x
82
Example 16
Step 3: Table 16.4 gives us
[H ][HC2O 4 ]
Ka =
[H 2C2O 4 ]
2
x
6.5 10-2 =
0.10 - x
0.10 - x
0.10
x 2 6.5 103
x = 8.1 102 M
83
Example 16
To test the approximation,
8.1 10-2 M
100% = 81%
0.10 M
84
Example 16
Step 4: When the equilibrium for the first stage of ionization is
reached, the concentrations are
[H+] = 0.054 M
[HC2O-4 ] = 0.054 M
[H2C2O4] = (0.10 - 0.054) M = 0.046 M
Next we consider the second stage of ionization.
Step 1: At this stage, the major species are HC2O-4 , which acts
as the acid in the second stage of ionization, H+, and
the conjugate base C2O24 .
85
Example 16
Step 2: Letting y be the equilibrium concentration of H+ and
ions in mol/L, we summarize:
C2O24
Initial (M):
Change (M):
Equilibrium (M):
HC2O-4(aq)
H+(aq) +
C2O24 (aq)
0.054
-y
0.054
+y
0.00
+y
0.054 - y
0.054 + y
[H ][C2O24 ]
Ka =
[HC2 O 4 ]
(0.054 + y )(y)
6.1 10 =
(0.054 - y )
-5
86
Example 16
Applying the approximation 0.054 + y 0.054 and 0.054 - y
0.054, we obtain
(0.054)(y)
= y = 6.1 10-5 M
(0.054)
6.1 10-5 M
100% = 0.11%
0.054 M
The approximation is valid.
87
Example 16
Step 4: At equilibrium,
[H2C2O4] = 0.046 M
[ HC2O-4 ] = (0.054 - 6.1 x 10-5) M = 0.054 M
[H+] = (0.054 + 6.1 x 10-5) M = 0.054 M
-5 M
[ C2O2]
=
6.1
x
10
4
[OH-] = 1.0 x 10-14/0.054 = 1.9 x 10-13 M
88
17.1
17.1
90
17.1
91
Example 17
17.1
92
Example 17
17.1
Setup
We use the stated concentration of acetic acid, 0.10 M,
and [H3O+] 0 M as the initial concentrations in the ice
table.
Solution
93
Example 17
17.1
x = 3.6 105 M.
[H3O+] = x, so pH = log (3.6 105) = 4.44
The common ion effect has shifted the ionization of
acetic acid to the left.
94
17.2
Buffer Solutions
95
17.2
Buffer Solutions
96
yes
yes
17.2
Buffer Solutions
99
17.2
Buffer Solutions
100
17.2
Buffer Solutions
101
17.2
Buffer Solutions
102
17.1
103
17.1
104
17.1
105
17.2
Buffer Solutions
17.2
Buffer Solutions
107
17.2
Buffer Solutions
Henderson-Hasselbalch equation
108
Example 18
17.2
109
Example 18
17.2
Setup
Solution
17.2
Buffer Solutions
111
17.2
Buffer Solutions
17.2
Buffer Solutions
113
17.2
Buffer Solutions
114
17.2
Buffer Solutions
115
17.3
Select an appropriate weak acid from the table, and
describe how you would prepare a buffer with a pH of
9.50.
116
17.3
Setup
Two of the acids listed in the table have pKa values in
the desired range: hydrocyanic acid (HCN, pKa = 9.31)
and phenol (C6H5OH, pKa = 9.89).
117
17.3
Solution
118
H+ (aq) + A- (aq)
OH- (aq) + HA (aq)
H+ (aq) + OH- (aq)
Ka
Kb
Kw
KaKb = Kw
Weak Acid and Its Conjugate Base
Kw
Ka =
Kb
Kw
Kb =
Ka
120
16.7
121
16.7
122
16.7
123
16.7
124
16.7
125
16.7
Ka
Kb
Kw
126
16.7
127
Example 19
16.17
Determine
(a) Kb of the acetate ion (CH3COO),
(b) Ka of the methylammonium ion (CH3NH3+ ),
(c) Kb of the fluoride ion (F), and
(d) Ka of the ammonium ion (NH4+ ).
Setup
128
Example 19
16.17
Solution
129
Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water
A Brnsted acid is a proton donor
A Lewis acid is a substance that can accept a pair of electrons
A Lewis base is a substance that can donate a pair of electrons
H+ + OH
acid base
H+ +
acid
H
N H
H
base
H O H
+
H N H
H
130
F B
N H
acid
base
F
F B
F
H
N H
H
131
Example 21
Identify the Lewis acid and Lewis base in each of the following
reactions:
(C2H5)2OAlCl3
Hg(CN)24 (aq)
132
Example 21
Strategy
In Lewis acid-base reactions, the acid is usually a cation or an
electron-deficient molecule, whereas the base is an anion or a
molecule containing an atom with lone pairs.
(a) Draw the molecular structure for C2H5OC2H5. What is the
hybridization state of Al in AlCl3?
(b) Which ion is likely to be an electron acceptor? An electron
donor?
133
Example 21
Solution
(a) The Al is sp2-hybridized in AlCl3 with an empty 2pz orbital. It
is electron deficient, sharing only six electrons. Therefore,
the Al atom has a tendency to gain two electrons to
complete its octet. This property makes AlCl3 a Lewis acid.
On the other hand, the lone pairs on the oxygen atom in
C2H5OC2H5 make the compound a Lewis base:
134
Example 21
(b) Here the Hg2+ ion accepts four pairs of electrons from the
CN- ions. Therefore, Hg2+ is the Lewis acid and CN- is the
Lewis base.
135