Acids and Bases

Topic 4 / Chapter 7

Acids
Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.

React with certain metals to produce hydrogen gas.

React with carbonates and bicarbonates to produce carbon
dioxide gas.

Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.

2

A Brnsted acid is a proton (H+) donor

A Brnsted base is a proton (H+) acceptor

base

acid

conjugate
acid

conjugate
base

There must be a proton acceptor before the acid releases its proton.

Gary Christian, Analytical Chemistry,

6th Ed. (Wiley)

16.1

Brnsted Acids and Bases

Brnsted Acids and Bases

16.1

Brnsted Acids and Bases

Brnsted Acids and Bases

16.1

Brnsted Acids and Bases

Brnsted Acids and Bases

16.1

Brnsted Acids and Bases

Brnsted Acids and Bases

Sample Problem 116.1

What is
(a) the conjugate base of HNO3,
(b) the conjugate acid of O2,
(c) the conjugate base of HSO4 , and
(d) the conjugate acid of HCO3 ?

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

Sample Problem 116.1

What is
(a) the conjugate base of HNO3,
(b) the conjugate acid of O2,
(c) the conjugate base of HSO4 , and
(d) the conjugate acid of HCO3 ?

Solution

10

16.2

The Acid-Base Properties of Water

A species that can behave either as a Brnsted acid or a

Brnsted base is called amphoteric.

11

Acid-Base Properties of Water

H+ (aq) + OH- (aq)

H2O (l)

autoionization of water
H

acid

+ H

[H

+ H

base
H2O + H2O

conjugate conjugate
acid
base
H3O+ + OH12

16.2

The Acid-Base Properties of Water

In pure water at 25C:

13

16.2

The Acid-Base Properties of Water

The relative amounts of H3O+ and OH determine

whether a solution is neutral, acidic, or basic.
When [H3O+] = [OH], the solution is neutral.
When [H3O+] > [OH], the solution is acidic.
When [H3O+] < [OH], the solution is basic.

14

The Ion Product of Water

H2O (l)

H+ (aq) + OH- (aq)

[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

[H+] > [OH-]

acidic

[H+] < [OH-]

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

[H+] > [OH-]

[H+] > 1.0 x 10-7

pH < 7

basic

[H+] < [OH-]

[H+] < 1.0 x 10-7

pH > 7

Solution Is
neutral

pH

[H+]
18

Other important relationships

pOH = -log [OH-]
[H+][OH-] = Kw = 1.0 x 10-14
-log [H+] log [OH-] = 14.00
pH + pOH = 14.00

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,

log [H+] = 4.82

To calculate [H+], we need to take the antilog of 4.82
[H+] = 104.82 = 1.5 x 105 M
24

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

Strong Electrolyte 100% dissociation

NaCl (s)

H2O

Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated

CH3COOH

CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

HCl (aq) + H2O (l)

H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l)

H3O+ (aq) + NO3- (aq)

HClO4 (aq) + H2O (l)

H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l)

H3O+ (aq) + HSO4- (aq)

28

Strong Bases are strong electrolytes

NaOH (s)
KOH (s)

H 2O
H 2O

Ba(OH)2 (s)

Na+ (aq) + OH- (aq)

K+ (aq) + OH- (aq)

H 2O

Ba2+ (aq) + 2OH- (aq)

29

16.4

Strong Acids and Bases

Strong Acids

Remember that although sulfuric acid has two ionizable

protons, only the first ionization is complete.
It is a good idea to commit this short list of strong acids
to memory.
30

16.4

Strong Acids and Bases

Strong Bases
Group 1A Hydroxides

Group 2A Hydroxides

31

Weak Acids are weak electrolytes

HF (aq) + H2O (l)

H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l)

H3O+ (aq) + NO2- (aq)

HSO4- (aq) + H2O (l)

H3O+ (aq) + SO42- (aq)

H2O (l) + H2O (l)

H3O+ (aq) + OH- (aq)

Weak Bases are weak electrolytes

F- (aq) + H2O (l)

NO2- (aq) + H2O (l)

OH- (aq) + HF (aq)

OH- (aq) + HNO2 (aq)

32

Conjugate acid-base pairs:

The conjugate base of a strong acid has no measurable

strength.

H3O+ is the strongest acid that can exist in aqueous

solution.

The OH- ion is the strongest base that can exist in aqueous
solution.

33

34

Strong Acid (HCl)

Weak Acid (HF)

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)

A positive (+) change represents an increase and a negative

(-) change indicates a decrease in concentration. Thus,
[H+] = 1.0 x 10-3 M
pH = -log (1.0 x 10-3)
= 3.00

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)

The changes in the concentrations of all the species can

be represented as follows:

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

Weak Acids (HA) and Acid Ionization Constants

HA (aq) + H2O (l)

HA (aq)

H3O+ (aq) + A- (aq)

H+ (aq) + A- (aq)
[H+][A-]
Ka =
[HA]

Ka is the acid ionization constant

Ka

weak acid
strength

51

 The Ionization Constant, Ka

52

Solving weak acid ionization problems:

1. Identify the major species that can affect the pH.

In most cases, you can ignore the autoionization of

water.

Ignore [OH-] because it is determined by [H+].

2. Use ICE to express the equilibrium concentrations in terms

of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve for x
by the approximation method. If approximation is not valid,
solve for x exactly.
4. Calculate concentrations of all species and/or pH of the
solution.
53

Example 10
Calculate the pH of a 0.036 M nitrous acid (HNO2) solution:
HNO2(aq)

H+(aq) + NO-2 (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.

As in Example 16.6, we ignore the ionization of H2O so the

major source of H+ ions is the acid. The concentration of OHions is very small as we would expect from an acidic solution so
it is present as a minor species.
55

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

Applying the approximation 0.036 - x 0.036, we obtain

2
2
x
x
4.5 10-4 =

0.036-x
0.036
x 2 1.62 105

x = 4.0 103 M
57

Example 10

Step 4: At equilibrium

[H+] = 3.8 x 10-3 M

pH = -log (3.8 x 10-3 )
= 2.42
Check Note that the calculated pH indicates that the solution is
acidic, which is what we would expect for a weak acid solution.
Compare the calculated pH with that of a 0.036 M strong acid
solution such as HCl to convince yourself of the difference
between a strong acid and a weak acid.

58

Example 11

16.12

The Ka of hypochlorous acid (HClO) is 3.5 108.

Calculate the pH of a solution at 25C that is 0.0075 M in
HClO.
Setup

59

Example 11

16.12

Setup

Solution

60

Example 11

16.12

Solution

61

16.5

Weak Acids and Acid Ionization Constants

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

Aspirin (acetylsalicylic acid, HC9H7O4) is a weak acid. It

ionizes in water according to the equation

A 0.10-M aqueous solution of

aspirin has a pH of 2.27 at 25C.
Determine the Ka of aspirin.

63

Example 12

16.14

Setup

Solution

64

Weak Bases and Base Ionization Constants

NH3 (aq) + H2O (l)

NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]
Kb is the base ionization constant
Kb

weak base
strength

Solve weak base problems like weak acids except solve

for [OH-] instead of [H+].
65

16.6

Weak Bases and Base Ionization Constants

The Ionization Constant, Kb

66

16.6

Weak Bases and Base Ionization Constants

The Ionization Constant, Kb

67

68

16.6

Weak Bases and Base Ionization Constants

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

What is the pH of a 0.040 M ammonia solution at 25C?

Setup

Solution

70

Example 13

16.15

Solution

71

Example 13

16.15

Solution

72

16.6

Weak Bases and Base Ionization Constants

Using pH to Determine Kb

Just as we can use pH to determine the Ka of a weak

acid, we can also use it to determine the Kb of a weak
base.

73

Example 14

16.16

Caffeine, the stimulant in coffee and tea, is a weak base

that ionizes in water according to the equation

A 0.15-M solution of caffeine at

25C has a pH of 8.45.
Determine the Kb of caffeine.

74

Example 14

16.16

Setup

Solution

75

16.5

Weak Acids and Acid Ionization Constants

Percent Ionization

76

Example 15

16.13

Determine pH and percent ionization for acetic acid

solutions at 25C with a concentration of 0.15 M
Setup
Ka for acetic acid is 1.8 105.

77

Example 15

16.13

Solution

78

Diprotic and Triprotic Acids

May yield more than one hydrogen ion per molecule.

Ionize in a stepwise manner; that is, they lose one proton at
a time.
An ionization constant expression can be written for each
ionization stage.
Consequently, two or more equilibrium constant expressions
must often be used to calculate the concentrations of
species in the acid solution.

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.

Step 2: Letting x be the equilibrium concentration of H+ and

HC2O-4 ions in mol/L, we summarize:

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

Applying the approximation 0.10 - x 0.10, we obtain

2
2
x
x
6.5 10-2 =

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

Clearly the approximation is not valid. Therefore, we must

solve the quadratic equation
x2 + 6.5 x 10-2x - 6.5 x 10-3 = 0
The result is x = 0.054 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

Step 3: Table 16.4 gives us

[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)

and we test the approximation,

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

The Common Ion Effect

The Common Ion Effect

Lets examine how the properties of a solution change
when a second solute is introduced.
Consider a liter of solution containing 0.10 mole of acetic
acid.

[H3O+] = [CH3COO] = 1.34 103 M and pH = 2.87

89

17.1

The Common Ion Effect

The Common Ion Effect

Now consider what happens when we add 0.050 mole of
sodium acetate (CH3COONa) to the solution.

90

17.1

The Common Ion Effect

The Common Ion Effect

In general, when a compound containing an ion in
common with a dissolved substance is added to a
solution at equilibrium, the ionization equilibrium shifts to
the left.

This phenomenon is known as the common ion effect.

The common ion can also be H3O+ or OH.

91

Example 17

17.1

Determine the pH at 25C of a solution prepared by

adding 0.050 mole of sodium acetate to 1.0 L of 0.10 M
acetic acid.

(Assume that the addition of sodium acetate does not

change the volume of the solution.)

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

Calculating the pH of a Buffer

Preparing a Buffer Solution with a Specific pH

95

17.2

Buffer Solutions

Calculating the pH of a Buffer

A solution that contains a weak acid and its conjugate
base (or a weak base and its conjugate acid) is a buffer
solution or simply a buffer.

96

yes

yes

17.2

Buffer Solutions

Calculating the pH of a Buffer

A buffers ability to convert a strong acid to a weak acid
minimizes the effect of the addition on the pH :
e.g. CH3COOH/ CH3COO- buffer

99

17.2

Buffer Solutions

Calculating the pH of a Buffer

A buffers ability to convert a strong base to a weak base
minimizes the effect of the addition on the pH :
e.g. CH3COOH/ CH3COO- buffer

100

17.2

Buffer Solutions

Calculating the pH of a Buffer

Suppose that we have 1 L of the 1.0 M acetic acid / 1.0
M sodium acetate buffer solution:

101

17.2

Buffer Solutions

Calculating the pH of a Buffer

102

17.1

The Common Ion Effect

Calculating the pH of a Buffer

Consider what happens when we add 0.10 mole of HCl
to the buffer.
(We assume that the addition of HCl causes no change
in the volume of the solution.)

103

17.1

The Common Ion Effect

Calculating the pH of a Buffer

A change of only 0.08 pH

units.

104

17.1

The Common Ion Effect

Calculating the pH of a Buffer

Had we added 0.10 mol of HCl to 1 L of pure water, the
pH would have gone from 7.00 to 1.00!

105

17.2

Buffer Solutions

Calculating the pH of a Buffer

In the determination of the pH of a buffer, we always
neglect the small amount of weak acid that ionizes (x)
because ionization is suppressed by the presence of a
common ion.
Similarly, we ignore the hydrolysis of the acetate ion
because of the presence of acetic acid.
This enables us to derive an expression for
determining the pH of a buffer.
106

17.2

Buffer Solutions

Calculating the pH of a Buffer

107

17.2

Buffer Solutions

Calculating the pH of a Buffer

Henderson-Hasselbalch equation
108

Example 18

17.2

Starting with 1.00 L of a buffer that is 1.00 M in acetic

acid and 1.00 M in sodium acetate, calculate the pH
after the addition of 0.100 mole of NaOH. (Assume that
the addition does not change the volume of the solution.)
Strategy

Added base will react with the acetic acid component of

the buffer, converting OH to CH3COO :
CH3COOH(aq) + OH(aq) H2O(l) + CH3COO(aq)

109

Example 18

17.2

Setup

Solution

Thus, the pH of the buffer after addition of 0.10 mol of

NaOH is 4.83.
110

17.2

Buffer Solutions

Preparing a Buffer Solution with a Specific pH

A solution is only a buffer if it has the capacity to resist
pH change when either an acid or a base is added.
If the concentrations of a weak acid and conjugate base
differ by more than a factor of 10, the solution does not
have this capacity.

111

17.2

Buffer Solutions

Preparing a Buffer Solution with a Specific pH

Therefore, we consider a solution a buffer, and can use

to calculate its pH, only if the following condition is met:

Consequently, the log term can only have values from

1 to 1, and the pH of a buffer cannot be more than one
pH unit different from the pKa of the weak acid it
contains.
112

17.2

Buffer Solutions

Preparing a Buffer Solution with as Specific pH

This is known as the range of the buffer, where pH = pKa
1.
This enables us to select the appropriate conjugate pair
to prepare a buffer with a specific, desired pH.

113

17.2

Buffer Solutions

Calculating the pH of a Buffer

To prepare a buffer with a specific, desired pH:
1. Choose a weak acid whose pKa is close to the
desired pH.

114

17.2

Buffer Solutions

Calculating the pH of a Buffer

2. Substitute the pH and pKa values into the following
equation to obtain the necessary ratio of [conjugate
base]/[weak acid].

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

One way to achieve this would be to dissolve 0.41 mol of

C6H5ONa and 1.00 mol of C6H5OH in 1 L of water.

118

Chemistry In Action: Antacids and the Stomach pH Balance

NaHCO3 (aq) + HCl (aq)

NaCl (aq) + H2O (l) + CO2 (g)

Mg(OH)2 (s) + 2HCl (aq)

MgCl2 (aq) + 2H2O (l)
119

Ionization Constants of Conjugate Acid-Base Pairs

HA (aq)
A- (aq) + H2O (l)
H2O (l)

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

Conjugate Acid-Base Pairs

The Strength of a Conjugate Acid or Base

The chloride ion, which is the conjugate base of a strong

acid, is an example of a weak conjugate base.

121

16.7

Conjugate Acid-Base Pairs

The Strength of a Conjugate Acid or Base

The fluoride ion, which is the conjugate base of a weak

acid, is an example of a strong conjugate base.
Conversely, a strong base has a weak conjugate acid
and a weak base has a strong conjugate acid.

122

16.7

Conjugate Acid-Base Pairs

The Strength of a Conjugate Acid or Base

123

16.7

Conjugate Acid-Base Pairs

The Strength of a Conjugate Acid or Base

124

16.7

Conjugate Acid-Base Pairs

The Relationship Between Ka and Kb of a Conjugate Acid-Base

Pair

125

16.7

Conjugate Acid-Base Pairs

The Relationship Between Ka and Kb of a Conjugate Acid-Base

Pair

Ka
Kb

Kw
126

16.7

Conjugate Acid-Base Pairs

The Relationship Between Ka and Kb of a Conjugate Acid-Base

Pair
Kb
Ka
Kw

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

Lewis Acids and Bases

F B

N H

acid

base

F
F B
F

H
N H
H

No protons donated or accepted!

131

Example 21
Identify the Lewis acid and Lewis base in each of the following
reactions:

(a) C2H5OC2H5 + AlCl3

(C2H5)2OAlCl3

(b) Hg2+(aq) + 4CN-(aq)

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