GENERAL CHEMISTRY

P R ı N C ı P L E S A N D M O D E R N A P P L ı C AT ı O N S
ELEVENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Acids and Bases 16

PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

Slide 16 - 1 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

Acids and Bases CONTENTS

16-1 Acids, Bases, and Conjugate

Acid-Base Pairs
16-2 Self Ionization of Water and the
pH Scale

16-3 Ionization of Acids and Bases in

Water

16-4 Strong Acids and Strong Bases

16-5 Weak Acids and Weak Bases
16-6 Polyprotic Acids
16-7 Qualitative Aspects of Acid-Base
Reactions

Slide 16 - 2 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

16-1 Acids, Bases, and Conjugate
Acid-Base Pairs

Brønsted-Lowry theory
An acid is a proton donor.
A base is a proton acceptor.

CH3COOH(aq) + H2O(aq) CH3COO− (aq) + H3O+(aq) (16.1)

Acid Base Base Acid

Slide 16 - 3 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

When CH3COOH loses a proton, it is converted into CH3COO-.
Species that differ by a single proton (H+) constitute a conjugate
acid-base pair. Within this pair, the species with the added H+ is the
acid, and the species without the H+ is the base.

Conjugate acid-base pair

CH3COOH(aq) + H2O(aq) CH3COO− (aq) + H3O+(aq) (16.2)

Acid Base Base Acid

Conjugate acid-base pair

An acid contains at least one ionizable H atom, and a base contains an

atom with a lone pair of electrons onto which a proton can bind.

Slide 16 - 4 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 Conjugate acid-base pair

NH3(aq) + H2O(aq) NH4+ (aq) + OH−(aq) (16.2)

Base Acid Acid Base

Conjugate acid-base pair

Slide 16 - 5 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

1A. For each of the following reactions, identify the acids and bases
in both the forward and reverse directions.
a) HF + H2O ⇌ F- + H3O+
b) HSO4- + NH3 ⇌ SO42-+ NH4+
c) CH3COO- + HCl ⇌ CH3COOH + Cl-

(a) In the forward direction, HF is the acid (proton donor; forms F), and H2O is the base
(proton acceptor; forms H3O+).
In the reverse direction, F is the base (forms HF),
accepting a proton from H3O+, which is the acid (forms H2O).
(b) In the forward direction, HSO4 is the acid (proton donor; forms SO42-), and NH3 is
the base (proton acceptor; forms NH4+).
In the reverse direction, SO42- is the base (forms HSO4), accepting a proton from NH4+,
which is the acid (forms NH3).
(c) In the forward direction, HCl is the acid (proton donor; forms Cl–), and CH3COO− is the
base (proton acceptor; forms CH3COOH).
In the reverse direction, Cl is the base (forms
HCl), accepting a proton from CH3COOH, which is the acid (forms CH3COO−).

Slide 16 - 6 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

16-2 Self-Ionization of Water and the pH Scale
H2O molecule can act as either an acid or a base; it is amphiprotic.
Amongst themselves water molecules can produce H3O+ and OH-
ions via the following self-ionization reaction or autoionization
reaction:

H2O(l) + H2O(l) H3O+ (aq) + OH−(aq)

In this reaction, one H2O molecule acts as an acid, another H2O

molecule acts as a base.

Slide 16 - 7 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 ion product of water

aH O+ (aq)aOH – (aq) ([H 3O+ ] / c°) ([OH – ] / c°) æ [H 3O+ ] ö æ [OH – ] ö

Kw = 3
= =ç
aH2 2O(l ) (1) 2
è 1 M ÷ø çè 1 M ÷ø

Kw = [H3O+]. [OH−]= 1.0 x 10-14 at 25⁰C

In pure water: [H 3O+ ] / (1 M) = [OH – ] / (1 M) = 1.0 ´10 –7 (at 25oC)

Since Kw is an equilibrium constant, the product of the

concentrations of the hydronium and hydroxide ions must always
equal 1.0×10-14.

Slide 16 - 8 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

pH and pOH

pH = −log[H3O+] = −log[H+]

pH = 4.5
[H3O+] = 2.5×10−3 M
log [H3O+] = −4.5
pH = −log(2.5×10−3) = 2.60 [H3O+] = 10−4.5 = 3.2×10−5

pOH = −log[OH−]

Slide 16 - 9 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 KW = [H3O+][OH−]

−logKW = −(log[H3O+]+log[OH−])

pKW = −(log[H3O+]+log[OH−])

= −log[H3O+] −log[OH−]

= pH + pOH

KW = 1.0×10−14 pKW = 14

pH + pOH = 14 (at 25ºC) (16.8)

Slide 16 - 10 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 Acidic, Basic, and Neutral Solutions
In pure water, the concentrations of H3O+ and OH- are equal.
However, when an acid or base is added to water, the H3O+ and OH-
ions are no longer present in equal amounts. By comparing the values
of [H3O+] and [OH-], we can classify a solution as acidic, basic, or
neutral.

Slide 16 - 11 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 FIGURE 16-4
Relating [H3O+], pH, [OH−], and pOH

Slide 16 - 12 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

2A. Students found that a yogurt sample had a pH of 2.85. What are
the [H+] and [OH-] of the yogurt?
pH = −log[H3O+] = 2.85

Slide 16 - 13 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

16-3 Ionization of Acids and Bases in Water
The ionization of HCl generates a higher [H3O+] than does the
ionization of CH3COOH, even though the initial molarity of
CH3COOH (0.1M) is greater than that of HCl (0.00to 0.07 M).
Ionization of HCl occurs to a greater extent than does the ionization
of CH3COOH, and indication that HCl is much stronger acid than
CH3COOH.
The strength of acid or base is quantified by the values of the
equilibrium constant for the reaction describing its ionization in
water.

Slide 16 - 14 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 HA(aq) + H2O(l) A− (aq) + H3O+(aq)

Ka: acid ionization constant

[H 3O+ ][A– ]
Ka =
[HA]
pK a = - log K a or Ka = 10- pKa

B(aq) + H2O(l) BH+ (aq) + OH−(aq)

Kb: base ionization constant

[BH + ][OH – ]
Kb =
[B]
pKb = - log Kb or Kb = 10- pKb

Slide 16 - 15 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

• A strong acid or base has a large ionization
constant:
Ka or Kb is very much greater than 1.
We can safely assume that a strong acid or base is
completely ionized in solution.
• A weak acid or base has a small ionization
constant:
Ka or Kb is much less than 1.
A significant fraction of the acid or base is not
ionized.

Slide 16 - 16 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

Slide 16 - 17 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.
Define the degree of ionization (α) for the ionization of an acid:

the molarity of A- from the ionization of HA

a= (16.15a)
initial molarity of HA

For the ionization of a base:

the molarity of BH + from the ionization of B

a= (16.15b)
initial molarity of B

percent ionization =100 ´ a (16.16)

In general, the degree of ionization (or the percent ionization) of

an acid or base in water depends on two factors: the value of the
ionization constant and the initial molarity.
Slide 16 - 18 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.
For a weak acid or a weak base, the degree of ionization increases with
increasing dilution.

HA(aq) + H2O(l) A− (aq) + H3O+(aq)

[H 3O+ ][A– ] (nH 3O+ / V) (nOH – /V) (nH 3O+ ) (nOH– ) æ 1 ö

Ka = = = ´ç ÷
[HA] (nHA / V) (nHA ) èVø

(nH O+ ) (nOH – )
as V increases, 3
must increase to maintain constant Ka.
(nHA )

Slide 16 - 19 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

4A. What is the percent ionization of hydrofluoric acid in 0.20 M
HF and in 0.020 M HF? Ka(HF)= 6.6 × 10-4

0.0036
% dissoc = x100 = 18 %
0.020
Slide 16 - 20 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.
16-4 Strong Acids and Strong Bases
A strong acid, such as HCl, is essentially completely ionized in
aqueous solution.
HCl(aq) + H2O(l) Cl− (aq) + H3O+(aq)
HCl is atrong acid and it is completely dissociated into its ions.

This means that: [HCl] = [Cl-] = [H3O+]

With strong bases, again complete dissociation occur.

Ca(OH)2(aq) Ca+ (aq) + 2OH−(aq)

[Ca(OH)2] = [Ca] = [OH]

Slide 16 - 21 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

5A) 0.0025 M solution of HI(aq) has [H3O+]=0.0025 M. Calculate
[I-] and [OH-] and the pH of the solution.

Slide 16 - 22 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

6A. Milk of magnesia is a saturated solution of Mg(OH)2. Its
solubility is 9.63 mg Mg(OH)2/100.0 mL solution at 20°C. What is
the pH of saturated Mg(OH)2 at 20°C? (Molar mass of Mg(OH)2
58.32 g/mol)

Slide 16 - 23 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 16-5 Weak Acids and Weak Bases
7A. 0.150 M solution of HOCl has a pH of 4.18. Determine Ka for
hypochlorous acid.

Slide 16 - 24 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

8B. Acetylsalicylic acid, HC9H7O4, is the active component in aspirin. Two extra-
strength aspirin tablets, each containing 500 mg of acetylsalicylic acid, are
dissolved in 325 mL of water. What is the pH of this solution? (Molar mass of
HC9H7O4 is 180.155 g/mol)

HC9H7O4(aq) + H2O(aq) H3O+(aq) + C9H7O4−(aq) Ka = 3.3 × 10-4

Slide 16 - 25 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

More on Simplifying Assumptions

The x << c assumption generally works if the concentration

of the weak acid, cA, or weak base, cB, exceeds the value of
Ka or Ka by a factor of at least 100.

cA (or cB )
If: > 100
K A (or K B )

You can assume x <<< c

Slide 16 - 26 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

16-6 Polyprotic Acids
Polyprotic acids acids have more than
one ionizable H atom per molecule.
The H3PO4 molecule has three
ionizable H atoms; it is a triprotic
acid. It ionizes in three steps.

Phosphoric acid, H3PO4

− [H 3O+ ][H 2 PO4 – ]

H3PO4 + H2O H3 O+ + H2PO4 K a1 = = 7.1´10 –3
[H 3PO 4 ]

[H 3O+ ][HPO4 2 – ]
−
H2PO4 + H2O H3 O+ + HPO4 2− K a2 = = 6.3 ´10 –8

[H 2 PO4 – ]

[H 3O+ ][PO 4 3– ]
HPO42− + H2O H3O+ + PO43− K a3 = 2–
= 4.2 ´10 –13
[HPO 4 ]
Slide 16 - 27 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.
For each step, we can write an ionization equation and an
acid ionization constant expression with a distinctive value of Ka.

Ka1>Ka2>Ka3

When ionization occurs in step (1), a proton (H+) moves away from
an ion with a 1- charge (H2PO4-).

In step (2), the proton moves away from an ion with a 2- charge
(HPO42-), a more difficult separation.

As a result, the ionization constant in the second step is smaller than

that in the first. Ionization is more difficult still in step (3).

Slide 16 - 28 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 H3PO4

Ka1 >> Ka2

All H3O+ is formed in the first ionization step.

H2PO4− essentially does not ionize further.

Assume [H2PO4−] = [H3O+].

[HPO42−] ≈ Ka2 regardless of solution molarity.

[H 3O+ ][HPO4 2 – ]
–
= K a2
[H 2 PO 4 ]

Slide 16 - 29 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

 10A. Malonic acid, HOOCCH2COOH, is a diprotic acid used in the manufacture
of barbiturates.
HOOCCH2COOH(aq)+H2O(aq) H3O+(aq)+HOOCCH2COO−(aq) Ka1=1.4×10-3
HOOCCH2COO−(aq)+H2O(aq) H3O+(aq)+ − OOCCH2COO−(aq) Ka2=2.0×10-6
Calculate [H3O+], [HOOCCH2COO−], and [− OOCCH2COO−] in a 1.00 M solution of
malonic acid.

Slide 16 - 30 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

The product of the ionization constants of an acid and its conjugate base
equals the ion product of water.

Ka (acid)×Kb (its conjugate base) = Kw

(16.20)
Kb (base)×Ka (its conjugate acid) = Kw

The conjugate of strong is extremely weak.

Slide 16 - 31 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

16-7 Qualitative Aspects of Acid-Base Reactions
HA + B A− + BH+
Acid Base Base Acid

For an acid-base reaction, equilibrium favors the formation of the weaker acid and
the weaker base.
CH3COOH + C5H5N CH3COO− + C5H5NH+

Acid(1) Base(2) Base(1) Acid(2)

Ka = 1.8×10−5 Kb = 1.5×10−9 Kb = 5.6×10−10 Ka = 6.7×10−6

Equilibrium favors the formation of CH3COO-, the weaker of the

two bases, and C5H5NH+, the weaker of the two acids.

Slide 16 - 32 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

If the acid or base in an acid-base reaction is strong, they react essentially to
completion.

Slide 16 - 33 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.