4/5/2012

1
Proton Transfer Equilibria
(Chapter 16)
In this section, we will discuss the
properties of proton transfer
equilibria.
AcidsandBases
16
16.1 Brnsted Acids and Bases
16.2 Molecular Structure and Acid Strength
Hydrohalic Acids
Oxoacids
Carboxylic Acids
16.3 The Acid-Base Properties of Water
16.4 The pH Scale
16.5 Strong Acids and Bases
Strong Acids
Strong Bases
16.6 Weak Acids and Acid Ionization Constants
The Ionization Constant, K
a
Calculating pH from K
a
Percent Ionization
Using pH to Determine K
a
16.7 Weak Bases and Base Ionization Constants
The Ionization Constant, K
b
Calculating pH from K
b
Using pH to Determine K
b
AcidsandBases
16
16.8 Conjugate Acid-Base Pairs
The Strength of a Conjugate Acid or Base
The Relationship Between K
a
and K
b
of a Conjugate Acid-Base
Pair
16.9 Diprotic and Polyprotic Acids
16.10 Acid-Base Properties of Salt Solutions
Basic Salt Solutions
Acidic Salt Solutions
Neutral Salt Solutions
Salts in Which Both the Cation and the Anion Hydrolyze
16.11 Acid-Base Properties of Oxides and Hydroxides
Oxides of Metals and Nonmetals
Basic and Amphoteric Hydroxides
16.12 Lewis Acids and Bases
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BrnstedAcidsandBases
When a Brnsted acid donates a proton, what remains of the acid is
known as a conjugate base.
The two species HCl and Cl

are known as a conjugate acid-base

pair or simply a conjugate pair.
16.1
HCl(aq) + H
2
O(l) H
3
O
+
(aq) + Cl

(aq)
Gains a proton
Loses a proton
acid base conjugate
acid
conjugate
base
BrnstedAcidsandBases
When a Brnsted base accepts a proton, the newly formed
protonated species is known as a conjugate acid.
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH

(aq)
acid base conjugate
acid
conjugate
base
Gains a proton
Loses a proton
WorkedExample16.1
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. The
word proton, in this context, refers to H
+
. Thus, the formula and the charge will
both be affected by the addition or removal of H
+
.
What is (a) the conjugate base on HNO
3
, (b) the conjugate acid of O
2-
, (c) the
conjugate base of HSO
4
-
, and (d) the conjugate acid of HCO
3
-
.
Solution (a) NO
3
-
(b) OH
-
(c) SO
4
2-
(d) H
2
CO
3
Think About It A species does not need to be what we think of as an acid in
order for it to have a conjugate base. For example, we would not refer to the
hydroxide ion (OH
-
) as an acid but it does have a conjugate base, the oxide ion
(O
2-
). Furthermore, a species that can either lose or gain a proton, such as
HCO
3
-
, has both a conjugate base (CO
3
2-
) and a conjugate acid (H
2
CO
3
).
4/5/2012
3
WorkedExample16.2
Strategy In each equation, the reactant that loses a proton is the acid and the
reactant that gains the proton is the base. Each product is the conjugate of one of
the reactants. Two species that differ only by a proton constitute a conjugate pair.
Label each of the species in the following equations as an acid, base, conjugate
base, or conjugate acid:
(a) HF(aq) + NH
3
(aq) F
-
(aq) + NH
4
+
(aq)
(b) CH
3
COO
-
(aq) + H
2
O(l) CH
3
COOH(aq) + OH
-
(aq)
Solution (a) HF loses a proton a becomes F
-
; NH
3
gains a proton and becomes
NH
4
+
.
HF(aq) + NH
3
(aq) F
-
(aq) + NH
4
+
(aq)
(b) CH
3
COO
-
gains a proton to become CH
3
COOH; H
2
O loses a proton to
become OH
-
.
CH
3
COO
-
(aq) + H
2
O(l) CH
3
COOH(aq) + OH
-
(aq)
acid base conjugate base conjugate acid
acid base conjugate base conjugate acid
MolecularStructureandAcidStrength
The strength of an acid is measured by its tendency to ionize.
Two factors influence ionization:
1) The strength of the HX bond
2) The polarity of the HX bond
16.2
HX H
+
+ X

HX
+
MolecularStructureandAcidStrength
Hydrohalic acid strength:
Biggest factor is bond strength.
Only HF is a weak acid.
HF << HCl < HBr < HI
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MolecularStructureandAcidStrength
Oxoacids:
An oxoacid contains hydrogen, oxygen, and a central nonmetal atom.
MolecularStructureandAcidStrength
To compare oxoacid strength, it is convenient to divide the oxoacids
into two groups:
1) Oxoacids having different central atoms that are from the same
group of the periodic table and that have the same oxidation
number.
HClO
3
> HBrO
3
Cl is more electronegative; the OH bond is more polar.
MolecularStructureandAcidStrength
To compare oxoacid strength, it is convenient to divide the oxoacids
into two groups:
2) Oxoacids having the same central atom, but different numbers of
oxygen atoms.
HClO
4
> HClO
3
> HClO
2
> HClO
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WorkedExample16.3
Strategy In each group, compare the electronegativies or oxidation numbers of
the central atoms to determine which OH bonds are the most polar. The more
polar the OH bond, the more readily it is broken and the stronger the acid.
Predict the relative strengths of the oxoacids in each of the following groups:
(a) HClO, HBrO, and HIO; (b) HNO
3
and HNO
2
.
Solution (a) In a group with different central atoms, we must compare
electronegativities. The electronegativities of the central atoms in this group
decrease as follows: Cl > Br > I.
Acid strength decreases as follows: HClO > HBrO > HIO
(b) These two acids have the same central atom but differ in the number of
oxygen atoms. In a group such as this, the greater the number of attached oxygen
atoms, the higher the oxidation number and the stronger the acid.
HNO
3
is stronger than HNO
2
.
TheAcidBasePropertiesofWater 16.3
A species that can behave either as a Brnsted acid or a Brnsted
base is called amphoteric.
The acid-base properties of water produces H
3
O
+
and OH

ions in equilibrium with water in a

reaction known as the autoionization of water.
The equilibrium expression for the autoionization of water is given by:
K
w
= [H
3
O
+
][OH

] = 1.0 x 10
14
(at 25C)
MolecularStructureandAcidStrength
An important group of organic acids is the carboxylic acids:
The strength of the acid depends on the nature of the R group.
Aceticacid(K
a
=1.8x10
5
) Chloroaceticacid(K
a
=1.4x10
3
)
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TheAcidBasePropertiesofWater
Since the product of the concentrations of H
3
O
+
and OH

is equal
to a constant, the relative amount of each obeys a fixed
relationship.
Depending on which ion concentration is in excess, the solution will be considered
acidic or basic.
When [H
3
O
+
] = [OH

], the solution is neutral

When [H
3
O
+
] > [OH

], the solution is acidic

When [H
3
O
+
] < [OH

], the solution is basic

K
w
= [H
3
O
+
][OH

] = 1.0 x 10
14
(at 25C)
WorkedExample16.4
Strategy Use the value of K
w
to determine [OH
-
] when [H
3
O
+
] = 0.10 M.
The concentration of hydronium ions in stomach acid is 0.10 M. Calculate the
concentration of hydroxide ions in stomach acid at 25C.
Solution K
w
= [H
3
O
+
][OH
-
] = 1.010
-14
at 25C. Rearranging to solve for [OH
-
],
[OH
-
] =
1.010
-14
[H
3
O
+
]
[OH
-
] =
1.010
-14
0.10
[OH
-
] = 1.010
-13
M
Think About It Remember that the equilibrium constants are temperature
dependent. The value of K
w
= 1.010
-14
only at 25C.
ThepHScale
The acidity of an aqueous solution depends on the concentration of
hydronium ions, [H
3
O
+
].
The pH of a solution is defined as the negative base-10 logarithm of
the hydronium ion concentration (in mol/L)
In pure water at 25C, [H
3
O
+
] = log1.0 x 10
7
pH = log(1.0 x 10
7
) = 7.00
pH is a dimensionless quantity.
16.4
pH = log[H
3
O
+
] [H
3
O
+
] = 10
pH
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ThepHScale
ThepHScale
WorkedExample16.5
Strategy Given [H
3
O
+
], use pH = log[H
3
O
+
] to solve for pH.
Determine the pH of a solution at 25C in which the hydronium ion
concentration is (a) 3.510
-4
M, (b) 1.710
-7
M, and (c) 8.810
-11
M.
Solution
(a) pH = log(3.510
-4
) = 3.46
(b) pH = log(1.710
-7
) = 6.77
(c) pH = log(8.810
-11
) = 10.06
Think About It When a hydronium ion concentration falls between two
benchmark concentrations in Table 16.4, the pH falls between the two
corresponding pH values. In part (c), for example, the hydronium ion
concentration (8.810
-11
M) is greater than 1.010
-11
Mbut less than
1.010
-10
M. Therefore, we expect the pH to be between 11.00 and 10.00.
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WorkedExample16.6
Strategy Given pH, use [H
3
O
+
] = 10
-pH
to calculate [H
3
O
+
].
Calculate the hydronium ion concentration in a solution at 25C in which the pH
is (a) 4.76, (b) 11.95, and (c) 8.01.
Solution
(a) [H
3
O
+
] = 10
-4.76
= 1.710
-5
M
(b) [H
3
O
+
] = 10
-11.95
= 1.110
-12
M
(c) [H
3
O
+
] = 10
-8.01
= 9.810
-9
M
ThepHScale
A pOH scale analogous to the pH scale can be defined as the
negative base-10 logarithm of the hydroxide ion concentration.
From the definition of pH and pOH:
pOH = log[OH

] [OH

] = 10
pOH
pH + pOH = 14.00
ThepHScale
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WorkedExample16.7
Strategy Given [OH
-
], use pOH = log[OH
-
] to calculate pOH.
Determine the pOH of a solution at 25C in which the hydroxide ion
concentration is (a) 3.710
-5
M, (b) 4.110
-7
M, and (c) 8.310
-2
M.
Solution
(a) pOH = log(3.710
-5
) = 4.43
(b) pOH = log(4.110
-7
) = 6.39
(c) pOH = log(8.310
-2
) = 1.08
Think About It Remember that the pOH scale is, in essence, the reverse of the
pH scale. On the pOH scale, numbers below 7 indicate a basic solution, whereas
number above 7 indicate an acidic solution. The pOH benchmarks (abbreviated in
Table 16.6) work the same way the pH benchmarks do. In part (a), for example, a
hydroxide ion concentration between 110
-4
M and 110
-5
M corresponds
to a pOH between 4 and 5.
WorkedExample16.8
Strategy Given pOH, use [OH
-
] = 10
-pOH
to calculate [OH
-
].
Calculate the hydroxide ion concentration in a solution at 25C in which the
pOH is (a) 4.91, (b) 9.03, and (c) 10.55.
Solution
(a) [OH
-
] = 10
-4.91
= 1.210
-5
M
(b) [OH
-
] = 10
-9.03
= 9.310
-10
M
(c) [OH
-
] = 10
-10.55
= 2.810
-11
M
Think About It Use the benchmark pOH values to determine whether these
solutions are reasonable. In part (a), for example, the pOH between 4 and 5
corresponds to [OH
-
] between 110
-4
Mand 110
-5
M.
StrongAcidsandBases
Strong acid dissociations are not treated as equilibria, rather as
processes that go to completion.
16.5
Hydrochloric acid HCl(aq) + H
2
O(l) H
3
O
+
(aq) + Cl

(aq)
HBr(aq) + H
2
O(l) H
3
O
+
(aq) + Br

(aq) Hydrobromic acid

HI(aq) + H
2
O(l) H
3
O
+
(aq) + I

(aq) Hydroiodic acid

HNO
3
(aq) + H
2
O(l) H
3
O
+
(aq) + NO
3

(aq) Nitric acid

HClO
3
(aq) + H
2
O(l) H
3
O
+
(aq) + ClO
3

(aq) Chloric acid

HClO
4
(aq) + H
2
O(l) H
3
O
+
(aq) + ClO
4

(aq) Perchloric acid

H
2
SO
4
(aq) + H
2
O(l) H
3
O
+
(aq) + HSO
4

(aq) Sulfuric acid

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WorkedExample16.9
Strategy HI, HNO
3
, and HClO
4
are all strong acids, so the concentration of
hydronium ions in each solution is the same as the stated concentration of the
acid. Use pH = log[H
3
O
+
] to calculate pH.
Calculate the pH of an aqueous solution at 25C that is (a) 0.035 M in HI, (b)
1.210
-4
Min HNO
3
, and (c) 6.710
-5
Min HClO
4
.
Solution
(a) [H
3
O
+
] = 0.035 M
pH = log(0.035) = 1.46
(b) [H
3
O
+
] = 1.210
-4
M
pH = log(1.210
-4
) = 3.92
(c) [H
3
O
+
] = 6.710
-5
M
pH = log(6.710
-5
) = 4.17
Think About It Again, note that when a hydronium ion
concentration falls between two of the benchmark concentrations in
Table 16.4, the pH falls between the two corresponding pH values.
In part (b), for example, the hydronium ion concentration of
1.210
-4
Mis greater than 110
-4
Mand less than 110
-3
M.
Therefore, we expect the pH to be between 4.00 and 3.00.
WorkedExample16.10
Strategy Use [H
3
O
+
] = 10
-pH
to convert from pH to [H
3
O
+
]. In a strong acid
solution, [H
3
O
+
] is equal to the acid concentration.
Calculate the concentration on HCl in a solution at 25C that has pH (a) 4.95,
(b) 3.45, and (c) 2.78.
Solution
(a) [HCl] = [H
3
O
+
] = 10
-4.95
= 1.110
-5
M
(b) [HCl] = [H
3
O
+
] = 10
-3.45
= 3.510
-4
M
(c) [HCl] = [H
3
O
+
] = 10
-2.78
= 1.710
-3
M
Think About It As pH decreases, acid concentration increases.
StrongAcidsandBases
The list of strong bases consists of the hydroxides of alkali metals
and the heaviest alkaline earth metals.
LiOH(aq) Li
+
(aq) + OH

(aq)
NaOH(aq) Na
+
(aq) + OH

(aq)
KOH(aq) K
+
(aq) + OH

(aq)
RbOH(aq) Rb
+
(aq) + OH

(aq)
CsOH(aq) Cs
+
(aq) + OH

(aq)
Ca(OH)
2
(aq) Ca
2+
(aq) + 2OH

(aq)
Sr(OH)
2
(aq) Sr
2+
(aq) + 2OH

(aq)
Ba(OH)
2
(aq) Ba
2+
(aq) + 2OH

(aq)
Group 1A hydroxides
Group 2A hydroxides
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WorkedExample16.11
Strategy LiOH, Ba(OH)
2
, and KOH are all strong bases. Use reaction
stoichiometry to determine the hydroxide ion concentration and pOH = log[OH
-
]
to determine pOH.
Calculate the pOH of the following aqueous solutions at 25C: (a) 0.013 M
LiOH, (b) 0.013 MBa(OH)
2
, and (c) 9.210
-5
MKOH.
Solution (a) The hydroxide ion concentration is simply equal to the
concentration of the base. Therefore, [OH
-
] = [LiOH] = 0.013 M.
pOH = log(0.013) = 1.89
(b) The hydroxide ion concentration is twice that of the base:
Ba(OH)
2
(aq) Ba
2+
(aq) + 2OH
-
(aq)
Therefore, [OH
-
] = 2[Ba(OH)
2
] = 2(0.013 M) = 0.026 M.
pOH = log(0.026) = 1.59
(c) The hydroxide ion concentration is equal to the concentration of the base.
Therefore, [OH
-
] = [KOH] = 9.210
-5
M.
pOH = log(9.210
-5
) = 4.04
WorkedExample16.12
Strategy Use pH + pOH = 14.00 to convert from pH to pOH and [OH
-
] =
10
-pOH
to determine the hydroxide ion concentration. Consider the stoichiometry
of dissociation in each case to determine the concentration of the base itself.
An aqueous solution of a strong base has pH 8.15 at 25C. Calculate the original
concentration of base in the solution (a) if the base is NaOH and (b) if the base is
Ba(OH)
2
.
Solution
pOH = 14.00 8.15 = 5.85
[OH
-
] = 10
-5.85
= 1.4110
-6
M
(a) The dissociation of 1 mole of NaOH produces 1 mole of OH-. Therefore, the
concentration of base is equal to the concentration of hydroxide ion.
[NaOH] = [OH
-
] = 1.4110
-6
M
(b) The dissociation of 2 mole of Ba(OH)
2
produces 2 moles of OH
-
. Therefore,
the concentration of base is only one-half the concentration of hydroxide ion.
[Ba(OH)
2
] = [OH
-
] = 7.110
-7
M
1
2
WeakAcidsandAcidIonizationConstants
The ionization of a weak monoprotic acid HA in water is represented by:
K
a
is called the acid ionization constant.
The larger the value of K
a
, the stronger the acid.
16.6
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A

(aq)
| |
+
3
a
H O A
HA
K

( (

=
Solution(at25C) K
a
pH
0.10MHF 7.1x10
4
2.09
0.10MCH
3
COOH 1.8x10
5
2.87
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WeakAcidsandAcidIonizationConstants
WeakAcidsandAcidIonizationConstants
Calculate the pH of a 0.50 M HF solution at 25C.
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
| |
+
3 4
a
H O F
7.1 10
HF
K

( (

= =
Initial concentration (M)
Change in concentration (M)
Equilibriumconcentration (M)
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
x
0.50 x
+x +x
x x
0.50
0 0
WeakAcidsandAcidIonizationConstants
| |
+
3
a
H O F
HF
K

( (

=
Initialconcentration (M) 0.50 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.50 x x x
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
( ) ( )
4
a
7.1 10
0.50
x x
K
x

= =

Use quadratic formula to solve

or
Since HF is a weak acid, x could be small
compared to 0.50
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WeakAcidsandAcidIonizationConstants
Initialconcentration (M) 0.50 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.50 x x x
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
( ) ( )
4
a
7.1 10
0.50
x x
K
x

= =

( ) ( )
4
a
7.1 10
0.50
x x
K

= =
x
2
=(0.50)(7.1 x 10
4
) =3.55 x 10
4
x = 1.9 x 10
2
simplifies
WeakAcidsandAcidIonizationConstants
Initialconcentration (M) 0.50 0 0
Changeinconcentration(M) 1.9x10
2
+1.9x10
2
+1.9x10
2
Equilibriumconcentration (M) 0.48 1.9x10
2
1.9x10
2
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
a
0.019
100% 3.8%
0.50
M
K
M
= =
pH =log(0.019) =1.72
The shortcut is acceptable to use if
the calculate value of x is less than
5% of the initial acid concentration
WorkedExample16.13
Strategy Construct an equilibrium table, and express the equilibrium and
concentration of each species in terms of x. Solve for x using the approximation
shortcut, and evaluate whether or not the approximation is valid. Use
pH = log[H
3
O
+
] to determine pH.
The Ka of hypochlorous acid (HClO) is 3.510
-8
. Calculate the pH of a solution
at 25C that is 0.0075 Min HClO.
Initialconcentration (M) 0.0075 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.0075 x x x
HClO(aq) + H
2
O(l) H
3
O
+
(aq) + ClO

(aq)
4/5/2012
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WorkedExample16.13(cont.)
Solution These equilibrium concentrations are then substituted into the
equilibrium expression to give
Assuming that 0.0075 x 0.0075,
Solving for x, we get
x = = 1.6210
-5
M
According to the equilibrium table, x = [H
3
O
+
]. Therefore,
pH = log(1.6210
-5
) = 4.79
K
a
=
(x)(x)
0.0075 x
= 3.510
-8
x
2
0.0075
= 3.510
-8
x
2
= (3.510
-8
)(0.0075)
10
10 625 . 2

WeakAcidsandAcidIonizationConstants
Initialconcentration (M) 0.50 0 0
Changeinconcentration(M) 1.9x10
2
+1.9x10
2
+1.9x10
2
Equilibriumconcentration (M) 0.48 1.9x10
2
1.9x10
2
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
A quantitative measure of the degree of ionization is percent
ionization.
| |
3
eq
0
H O
percent ionization 100%
HA
+
(

=
0.019
percent ionization 100% 3.8%
0.50
M
M
= =
WeakAcidsandAcidIonizationConstants
Initialconcentration (M) 1.00 0 0
Changeinconcentration(M)
Equilibriumconcentration (M)
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
0.027
percent ionization 100% 2.7%
1.0
M
M
= =
Solution(at25C) pH %ionization
0.5M HF 1.72 3.8
1.0M HF 1.57 2.7
Calculate the percent ionization of a 1.0 M HF solution at 25C.
2.7 x 10
2
+2.7 x 10
2
+2.7 x 10
2
2.7 x 10
2
2.7 x 10
2
0.97
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WeakAcidsandAcidIonizationConstants
HF(aq) + H
2
O(l) H
3
O
+
(aq) + F

(aq)
Solution(at25C) pH %ionization
0.5M HF 1.72 3.8
1.0M HF 1.57 2.7
WorkedExample16.14
Strategy Using the procedure described in Worked Example 16.13, we
construct an equilibrium table and for each concentration of acetic acid, we solve
for the equilibrium concentration of H
+
. We use pH = log[H
3
O
+
] to find pH, and
the equation below to find percent ionization. K
a
for acetic acid is 1.810
-5
.
Determine the pH and percent ionization for acetic acid solutions at 25C with
concentrations (a) 0.15 M, (b) 0.015 M, and (c) 0.0015 M.
| |
3
eq
0
H O
percent ionization 100%
HA
+
(

=
WorkedExample16.14(cont.)
Solution (a)
Solving for x gives [H
3
O
+
] = 0.0016 Mand pH = log(0.0016) = 2.78.
(b) Solving the same way as part (a) gives [H
3
O
+
] = 5.210
-4
Mand pH = 3.28.
Initialconcentration (M) 0.15 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.15 x x x
CH
3
COOH(aq) + H
2
O(l) H
3
O
+
(aq) + CH
3
COO

(aq)
0.0016 M
0.15 M
percent ionization = 100% = 1.1%
5.210
-4
M
0.015 M
percent ionization = 100% = 3.5%
4/5/2012
16
WorkedExample16.14(cont.)
Solution (c) Solving the quadratic equation, or using successive approximation
[Appendix 1] gives [H
3
O
+
] = 1.610
-4
Mand pH = 3.78.
1.610
-4
M
0.0015 M
percent ionization = 100% = 11%
Think About It Check your work by using the calculated value of K
a
to solve
for the pH of a 0.10-Msolution of aspirin.
WeakAcidsandAcidIonizationConstants
Determine the K
a
of a weak acid that has a concentration of 0.25 M
and a pH of 3.47 at 25C.
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A

(aq)
| |
+
3
a
H O A
?
HA
K

( (

= =
Initialconcentration (M) 0.25 0 0
Changeinconcentration(M)
Equilibriumconcentration (M)
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A

(aq)
0.2497 3.39 x 10
4
3.39 x 10
4
+3.39 x 10
4
+3.39 x 10
4
3.39 x 10
4
H
3
O
+
= 10
3.47
= 3.39 x 10
4
M
WeakAcidsandAcidIonizationConstants
Determine the K
a
of a weak acid that has a concentration of 0.25 M and a
pH of 3.47 at 25C.
Initialconcentration (M) 0.25 0 0
Changeinconcentration(M)
Equilibriumconcentration (M)
HA(aq) + H
2
O(l) H
3
O
+
(aq) + A

(aq)
0.2497 3.39 x 10
4
3.39 x 10
4
+3.39 x 10
4
+3.39 x 10
4
3.39 x 10
4
| |
+
3
a
H O A
HA
K

( (

=
( )
2
4
7
a
3.39 10
4.6 10
0.2497
K

= =
4/5/2012
17
WorkedExample16.15
Strategy Determine the hydronium ion concentration from the pH. Use the
hydronium ion concentration to determine the equilibrium concentrations of the
other species, and plug the equilibrium concentrations into the equilibrium
expressions to evaluate K
a
.
Aspirin (acetylsalicylic acid, HC
9
H
7
O
4
) is a weak acid. It ionizes in water
according to the equation
HC
9
H
7
O
4
(aq) + H
2
O(l) H
3
O
+
(aq) + C
9
H
7
O
4
-
(aq)
A 0.10-Maqueous solution of aspirin has a pH of 2.27 at 25C. Determine the
K
a
of aspirin.
WorkedExample16.15(cont.)
Solution [H
3
O
+
] = 10
2.27
= 5.3710
-3
M
To calculate K
a
, though, we also need the equilibrium concentrations of C
9
H
7
O
4
-
and HC
9
H
7
O
4
. The stoichiometry of the reaction tells us that [C
9
H
7
O
4
-
] = [H
3
O
+
].
Furthermore, the amount of aspirin that has ionized is equal to the amount of
hydronium ion in solution. Therefore, the equilibrium concentration of aspirin is
(0.10 5.3710
-3
) M= 0.095 M.
The K
a
of aspirin is 3.010
-4
.
Initialconcentration (M) 0.10 0 0
Changeinconcentration(M) 0.005 +5.3710
3
+5.3710
3
Equilibriumconcentration (M) 0.095 5.3710
3
5.3710
3
HC
9
H
7
O
4
(aq) + H
2
O(l) H
3
O
+
(aq) + C
9
H
7
O
4
-
(aq)
K
a
=
[H
3
O
+
][C
9
H
7
O
4
-
]
[HC
9
H
7
O
4
]
= 3.010
-4
=
(5.3710
-3
)
2
0.095
WeakBasesandBaseIonizationConstants
The ionization of a weak base is incomplete and is treated in the same way as the ionization
of a weak acid.
K
b
is called the base ionization constant.
The larger the value of K
b
, the stronger the base.
16.7
B(aq) + H
2
O(l) HB
+
(aq) + OH

(aq)
| |
+
b
HB OH
B
K

( (

=
4/5/2012
18
WorkedExample16.16
Strategy Construct an equilibrium table, and express equilibrium concentrations
in terms of the unknown x. Plug these equilibrium concentrations into the
equilibrium expression, and solve for x. From the value of x, determine the pH.
What is the pH of a 0.040 Mammonia solution at 25C.
Initialconcentration (M) 0.040 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.040 x x x
NH
3
(aq) + H
2
O(l) NH
4
+
(aq) + OH
-
(aq)
WorkedExample16.16(cont.)
Solution The equilibrium concentrations are substituted into the equilibrium
expression to give
Assuming that 0.040 x 0.040 and solving for x gives
x
2
= (1.810
-5
)(0.040) = 7.210
-7
x = = 8.510
-4
M
According to the equilibrium table, x = [OH
-
]. Therefore, pOH = log(x):
log(8.510
-4
) = 3.07
and pH = 14.00 pOH = 14.00 3.07 10.93. The pH of a 0.040-Msolution of
NH
3
at 25C is 10.93.
K
b
=
[NH
4
+
][OH
-
]
[NH
3
]
= 1.810
-5
=
(x)(x)
0.040 x
= 1.810
-5
(x)(x)
0.040 x

(x)(x)
0.040
7
10 2 . 7

WeakBasesandBaseIonizationConstants
4/5/2012
19
WorkedExample16.17
Strategy Use pH to determine pOH, and pOH to determine the hydroxide ion
concentration. From the hydroxide ion concentration, use reaction stoichiometry
to determine the other equilibrium concentrations and plus those concentrations
into the equilibrium expression to evaluate K
b
.
Caffeine, the stimulant in coffee and tea, is a weak base that ionizes in water
according to the equation
C
8
H
10
N
4
O
2
(aq) + H
2
O(l) HC
8
H
10
N
4
O
2
+
(aq) + OH
-
(aq)
A 0.15-Msolution of caffeine at 25C has a pH of 8.45. Determine the K
b
of
caffeine.
WorkedExample16.17(cont.)
Solution pOH = 14.00 8.45 5.55; [OH
-
] = 10
-5.55
= 2.8210
-6
M
Based on the reaction stoichiometry, [HC
8
H
10
N
4
O
2
+
] = [OH
-
], and the amount of
hydroxide ion in solution at equilibrium is equal to the amount of caffeine that has
ionized. At equilibrium, therefore,
[C
8
H
10
N
4
O
2
] = (0.15 2.8210
-6
) M 0.15 M
K
b
=
[HC
8
H
10
N
4
O
2
+
][OH
-
]
[C
8
H
10
N
4
O
2
]
= 5.310
-11 =
(2.8210
-6
)
2
0.15
Initialconcentration (M) 0.15 0 0
Changeinconcentration(M) 2.8210
6
+2.8210
6
+2.8210
6
Equilibriumconcentration (M) 0.15 2.8210
6
2.8210
6
C
8
H
10
N
4
O
2
(aq) + H
2
O(l) HC
8
H
10
N
4
O
2
+
(aq) + OH
-
(aq)
ConjugateAcidBasePairs
A strong acid ionizes completely in water:
16.8
HCl(aq) H
+
(aq) + Cl

(aq)
No affinity for
the H
+
ion
Cl

(aq) + H
2
O(l) HCl(aq) + OH

(aq) X
The chloride ion is a weak conjugate base.
4/5/2012
20
ConjugateAcidBasePairs
A weak acid ionizes to a limited degree in water:
HF(aq) H
+
(aq) + F

(aq)
Strong affinity
for the H
+
ion
F

(aq) + H
2
O(l) HF(aq) + OH

(aq)
The fluoride ion is a strong conjugate base.
ConjugateAcidBasePairs
A strong acid has a weak conjugate base.
A weak acid has a strong conjugate base.
A strong base has a weak conjugate acid.
A weak base has a strong conjugate base.
ConjugateAcidBasePairs
A simple relationship between the ionization constant of a weak acid
(K
a
) and the ionization constant of a weak base (K
b
) can be derived:
CH
3
COOH(aq) H
+
(aq) + CH
3
COO

(aq)
CH
3
COO

(aq) + H
2
O(l) CH
3
COOH(aq) + OH

(aq)
H
2
O(l) H
+
(aq) + OH

(aq)
| |
+
3
a
3
H CH COO
CH COOH
K

( (

=
| |
3
b
3
CH COOH OH
CH COO
K

(

=
(

| |
| |
+
3 3
3 3
H CH COO CH COOH OH
H OH
CH COOH CH COO

+

( ( (

( ( =

(

K
a
x K
b
= K
w
4/5/2012
21
WorkedExample16.18
Strategy Each species listed is either a conjugate base or a conjugate acid.
Determine the identity of the acid corresponding to each conjugate base and the
identity of the base corresponding to each conjugate acid; then, consult Table 16.7
and 16.8 for their ionization constants. Use the tabulated ionization constants and
K
w
= K
a
K
b
to calculate each indicated K value.
Determine (a) K
b
of the acetate ion (CH
3
COO
-
), (b) K
a
of the methylammonium
ion (CH
3
NH
3
+
), (c) K
b
of the fluoride (F
-
), and (d) K
a
of the ammonium ion
(NH
4
+
).
Solution (a) A K
b
value is requested, indicating that the acetate ion is a
conjugate base. To identify the corresponding Brnsted acid, add a proton to the
formula to get CH
3
COOH (acetic acid). The K
a
of acetic acid is 1.810
-5
.
Conjugate base CH
3
COO
-
: K
b
= = 5.610
-10
1.010
-14
1.810
-5
K
w
K
b
K
a
=
K
w
K
a
K
b
= and
WorkedExample16.18(cont.)
Solution (b) A K
a
value is requested, indicating that the methylammonium ion is
a conjugate acid. Determine the identity of the corresponding Brnsted base by
removing a proton from the formula to get CH
3
NH
2
(methylamine). The K
b
of
methylamine is 4.410
-4
.
Conjugate acid CH
3
NH
3
+
: K
a
=
(c) F
-
is the conjugate base of HF; Ka = 7.110
-4
.
Conjugate base F
-
: K
b
=
(d) NH
4
+
is the conjugate acid of NH
3
; K
b
= 1.810
-5
.
Conjugate acid NH
4
+
: K
a
=
= 2.310
-11
1.010
-14
4.410
-4
= 1.410
-11
1.010
-14
7.110
-4
= 5.610
-10
1.010
-14
1.810
-5
DiproticandPolyproticAcids
Diprotic and polyprotic acids undergo successive ionizations, losing
one proton at a time, and each has a K
a
associate with it.
K
a1
> K
a2
For a given acid, the first ionization constant is much larger than the
second, and so on.
16.9
H
2
CO
3
(aq) H
+
(aq) + HCO
3

(aq)
HCO
3

(aq) H
+
(aq) + CO
3
2
(aq)
+ 2
3
a2
3
H CO
HCO
K

( (

=
(

| |
+
3
a1
2 3
H HCO
H CO
K

( (

=
4/5/2012
22
DiproticandPolyproticAcids
WorkedExample16.19
Strategy Follow the same procedure for each ionization as for the determination
of equilibrium concentrations for a monoprotic acid. The conjugate base resulting
from the first ionization is the acid for the second ionizations, and its starting
concentration is the equilibrium concentration from the first ionization.
H
2
C
2
O
4
(aq) H
+
(aq) + HC
2
O
4

(aq) K
a1
= 6.5 x 10
2
HC
2
O
4

(aq) H
+
(aq) + C
2
O
4
2
(aq) K
a2
= 6.1 x 10
5
Construct an equilibrium table for each ionization, using x as the unknown in the
first ionization and y as the unknown in the second ionization.
Oxalic acid (H
2
C
2
O
4
) is a poisonous substance used mainly as a bleaching agent.
Calculate the concentrations of all species present at equilibrium in a 0.10-M
solution at 25C.
WorkedExample16.19(cont.)
Strategy
The equilibrium concentration of the hydrogen oxalate (HC
2
O
4
-
) after the first
ionization becomes the starting concentration for the second ionization.
Additionally, the equilibrium concentration of H
+
is the starting concentration for
the second ionization.
Initialconcentration (M) 0.10 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.10 x x x
H
2
C
2
O
4
(aq) H
+
(aq) + HC
2
O
4

(aq)
Initialconcentration (M) x x 0
Changeinconcentration(M) y +y +y
Equilibriumconcentration (M) x y x+y y
HC
2
O
4

(aq) H
+
(aq) + C
2
O
4
2
(aq)
4/5/2012
23
WorkedExample16.19(cont.)
Solution
Applying the approximation and neglecting x in the denominator of the
expression gives
Testing the approximation,
Clearly the approximation is not valid, so we must solve the following quadratic
equation:
x
2
+ 6.510
-3
x 6.510
-3
= 0
6.510
-2
=
[H
+
][HC
2
O
4
-
]
[H
2
C
2
O
4
]
K
a1
=
x
2
0.10 x
6.510
-2

x
2
0.10
x
2
= 6.510
-3
x = 8.110
-2
M
8.110
-2
M
0.10 M
100% = 81%
WorkedExample16.19(cont.)
Solution The result x = 0.054 M. Thus, after the first ionization, the
concentrations of species in solution are
[H
+
] = 0.054 M
[HC
2
O
4
-
] = 0.054 M
[H
2
C
2
O
4
] = (0.10 0.054) M= 0.046 M
Rewriting the equilibrium table for the second ionization, using the calculated
value of x, gives the following:
6.110
-5
=
[H
+
][C
2
O
4
2-
]
[HC
2
O
4
-
]
K
a2
=
(0.054 + y)(y)
0.054 y
Initialconcentration (M) 0.054 0.054 0
Changeinconcentration(M) y +y +y
Equilibriumconcentration (M) 0.054 y 0.054 +y y
HC
2
O
4

(aq) H
+
(aq) + C
2
O
4
2
(aq)
WorkedExample16.19(cont.)
Solution Assuming that y is very small and applying the approximations
0.054 + y 0.054 and 0.054 y 0.054 gives
We must test the approximation as follows to see if it is valid:
This time, because the ionization constant is much smaller, the approximation is
valid. At equilibrium, the concentrations of all species are
[H
2
C
2
O
4
] = 0.046 M
[HC
2
O
4
-
] = (0.054 6.110
-5
) = 0.054 M
[H
+
] = (0.054 + 6.110
-5
) = 0.054 M
[C
2
O
4
2-
] = 6.110
-5
M
= y = 6.110
-5
(0.054)(y)
0.054
6.110
-5
M
0.054 M
100% = 0.11%
4/5/2012
24
AcidBasePropertiesofSaltSolutions
Salt hydrolysis occurs when ions produced by the dissociation of a
salt react with water to produce either hydroxide ions or hydronium
ions.
Basic salts (conjugates of weak acids):
Acidic salts (conjugates of weak bases)
16.10
F

(aq) + H
2
O(l) HF(aq) + OH

(aq)
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
WorkedExample16.20
Strategy A solution of NaF contains Na
+
ions and F
-
ions. The F
-
ion is the
conjugate base of the weak acid, HF. Use the K
a
value for HF (7.110
-4
) and
K
w
= K
b
K
a
to determine K
b
for F
-
:
Then, solve this pH problem like any equilibrium problem, using an equilibrium
table.
F
-
(aq) + H
2
O(l) HF(aq) + OH
-
(aq)
Calculate the pH of a 0.10-Msolution of sodium fluoride (NaF) at 25C.
= 1.410
-11
1.010
-14
7.110
-4
K
w
K
a
K
b
= =
[HF][OH
-
]
[F
-
]
K
b
=
F
-
(aq) + H
2
O(l) HF(aq) + OH
-
(aq)
Initialconcentration (M) 0.10 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.10 x x x
WorkedExample16.20(cont.)
Solution Substituting the equilibrium concentrations into the equilibrium
expression and using the shortcut to solve x, we get
According to our equilibrium table, x = [OH
-
]. In this case, the autoionization of
water makes a significant contribution to the hydroxide ion concentration so the
total concentration will be the sum of 1.210
-6
M(from the ionization of F
-
) and
1.010
-7
M(from the autoionization of water). Therefore, we calculate the pOH
first as
pOH = log(1.210
-6
+ 1.010
-7
) = 5.95
and then the pH,
pH = 14.00 pOH = 14.00 5.95 = 8.05
The pH of a 0.10-Msolution of NaF at 25C is 8.05.
1.410
-11
=
x
2
0.10 x
x
2
0.10

x = = 1.210
-6
M ) 10 . 0 )( 10 4 . 1 (
11

4/5/2012
25
WorkedExample16.21
Strategy A solution of NH
4
Cl contains NH
4
+
ions and Cl
-
ions. The NH
4
+
ion is
the conjugate acid of the weak base, NH
3
. Use the K
b
value for NH
3
(1.810
-5
)
and K
w
= K
b
K
a
to determine K
a
for F
-
:
Again, we write the balanced chemical equation and the equilibrium expression:
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
Calculate the pH of a 0.10-Msolution of ammonium chloride (NH
4
Cl) at 25C.
= 5.610
-10
1.010
-14
1.810
-5
K
w
K
b
K
a
= =
[NH
3
][H
3
O
+
]
[NH
4
+
]
K
b
=
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
Initialconcentration (M) 0.10 0 0
Changeinconcentration(M) x +x +x
Equilibriumconcentration (M) 0.10 x x x
WorkedExample16.21(cont.)
Solution Substituting the equilibrium concentrations into the equilibrium
expression and using the shortcut to solve x, we get
According to our equilibrium table, x = [H
3
O
+
]. The pH can be calculated as
follows:
pH = log(7.510
-6
) = 5.12
The pH of a 0.10-Msolution of ammonium chloride (at 25C) is 5.12.
5.610
-10
=
x
2
0.10 x
x
2
0.10

x = = 7.510
-6
M ) 10 . 0 )( 10 6 . 5 (
10

Think About It In this case, we would predict an acidic pH because the cation
in the salt (NH
4
+
) is the conjugate acid of a weak base (NH
3
). The calculated pH
is acidic.
AcidBasePropertiesofSaltSolutions
Small, highly charged metal ions can react with water to produce an
acidic solution.
4/5/2012
26
AcidBasePropertiesofSaltSolutions
The pH of salt solutions can be qualitatively predicted by
determining which ions facilitate hydrolysis.
Examples
Acation thatwillmakeasolutionacidicis
Theconjugateacidofaweakbase
Asmall,highlychargedmetalion(otherthanGroup 1A
or2A)
NH
4
+
,CH
3
NH
3
+
,C
2
H
5
NH
3
+
Al
3+
,Cr
3+
,Fe
3+
,Bi
3+
Ananionthatwillmakeasolutionbasic is
Theconjugatebaseofaweakacid CN

,NO
2
,CH
3
COO

Acation thatwillnotaffectthepHofasolutionis
AGroup 1AorheavyGroup2Acation (exceptBe
2+
) Li
+
,Na
+
,Ba
2+
AnanionthatwillnotaffectthepHofasolutionis
Theconjugatebaseofastrongacid Cl

,NO
3

,ClO
4

WorkedExample16.22
Strategy Identify the ions present in each solution, and determine which, if any,
will impact the pH of the solution.
Predict whether a 0.10-Msolution of each of the following salts will be basic,
acidic, or neutral: (a) LiI, (b) NH
4
NO
3
, (c) Sr(NO
3
)
2
, (d) KNO
2
, (e) NaCN.
Solution (a) Ions in solution: Li
+
and I
-
. Li
+
is a Group 1A cation; I
-
is the
conjugate base of the strong acid HI. Therefore, neither ion hydrolyzes to any
significant degree. Solution will be neutral.
(b) Ions in solution: NH
4
+
and NO
3
-
. NH
4
+
is the conjugate acid of the weak base
NH
3
; NO
3
-
is the conjugate base of the strong acid HNO
3
. In this case, the cation
will hydrolyze, making the pH acidic:
NH
4
+
(aq) + H
2
O(l) NH
3
(aq) + H
3
O
+
(aq)
WorkedExample16.22(cont.)
Solution (c) Ions in solution: Sr
2+
and NO
3
-
. Sr
2+
is a heavy Group 2A cation;
NO
3
-
is the conjugate base of the strong acid, HNO
3
. Neither ion hydrolyzes to
any significant degree.
(d) Ions in solution: K
+
and NO
2
-
. K
+
is a Group 1A cation; NO
2
-
is the conjugate
base of the weak acid HNO
2
. In this case, the anion hydrolyzes, thus making the
pH basic:
NO
2
-
(aq) + H
2
O(l) HNO
2
(aq) + OH
-
(aq)
(e) Ions in solution: Na
+
and CN
-
. Na
+
is a Group 1A cation; CN
-
is the conjugate
base of the weak acid HCN. In this case, too, the anion hydrolyzes, thus making
the pH basic:
CN
-
(aq) + H
2
O(l) HCN(aq) + OH
-
(aq)
Think About It Its very important that you be able to identify the ions in
solution correctly. If necessary, review the formulas and charges of the common
polyatomic ions.
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27
AcidBasePropertiesofSaltSolutions
The pH of a solution that contains a salt in which both the cation and the anion hydrolyze
depends on the relative strengths of the weak acid and base.
Qualitative predictions can be made using the K
b
(of the salts anion) and the K
a
(of the salts
cation).
When K
b
> K
a
, the solution is basic
When K
b
< K
a
, the solution is acidic
When K
b
K
a
, the solution is neutral or nearly neutral
AcidBasePropertiesofOxidesandHydroxides 16.11
AcidBasePropertiesofOxidesandHydroxides
Basic metallic oxides react with water to form metal hydroxides:
Na
2
O(s) + H
2
O(l) 2NaOH(aq)
BaO(s) + H
2
O(l) Ba(OH)
2
(aq)
Acidic oxides reaction with water as follows:
CO
2
(g) + H
2
O(l) H
2
CO
3
(aq)
SO
3
(g) + H
2
O(l) H
2
SO
4
(aq)
Reactions between acidic oxides and bases and those between basic oxides and acids
resemble normal acid-base reactions that produce a salt and water.
CO
2
(g) + 2NaOH(aq) Na
2
CO
3
(aq) + H
2
O(l)
BaO(s) + 2HNO
3
(aq) Ba(NO
3
)
2
(aq) + H
2
O(l)
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28
AcidBasePropertiesofOxidesandHydroxides
Aluminum oxide (Al
2
O
3
) is amphoteric.
It can act as an acid:
Al
2
O
3
(s) + 6HCl(aq) 2AlCl
3
(aq) + 3H
2
O(l)
Or it can act as a base:
Al
2
O
3
(s) + 2NaOH(aq) + 3H
2
O(l) 2NaAl(OH)
4
(aq)
AcidBasePropertiesofOxidesandHydroxides
All the alkali and alkaline earth metal hydroxides, except Be(OH)
2
,
are basic.
Be(OH)
2
Al(OH)
3
Sn(OH)
2
Pb(OH)
2
Cr(OH)
3
Cu(OH)
2
Zn(OH)
2
Cd(OH)
2
Acid:
Be(OH)
2
(s) + 6H
+
(aq) 2Be
2+
(aq) + 2H
2
O(l)
Base:
Be(OH)
2
(s) + 2OH

(aq) Be(OH)
4
2
(aq)
amphoteric
LewisAcidsandBases
A Lewis base is a substance that can donate a pair of electrons.
A Lewis acid is a substance that can accept a pair of electrons.
16.12
Ammonia,
a Lewis base
Boron trifluoride
a Lewis acid
empty
unhybridized 2p
z
orbital
F
B
F
F
N
H
H
H
N
H
H
H
B
F
F
F
A coordinate covalent bond
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29
AcidsandBases
16
Brnsted Acids and Bases
The Acid-Base Properties of Water
The pH Scale
Strong Acids and Bases
The Ionization Constant, K
a
Calculating pH from K
a
Using pH to Determine K
a
The Ionization Constant, K
b
Calculating pH from K
b
Using pH to Determine K
b
The Strength of a Conjugate Acid or Base
The Relationship Between K
a
and K
b
of a Conjugate Acid-Base Pair
Diprotic and Polyprotic Acids
Hydrohalic Acids
Oxoacids
Carboxylic Acids
Basic Salt Solutions
Acidic Salt Solutions
Neutral Salt Solutions
Salts in Which Both the Cation and the
Anion Hydrolyze
Oxides of Metals and Nonmetals
Basic and Amphoteric Hydroxides
Lewis Acids and Bases