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Chapter 15: Acid-Base Equilibria in Aqueous Solution

Lecture 1

• Understanding the properties of acids and bases

• Practicing the calculations with acid dissociation constant
• Understanding and applying the pH and pOH calculations
• Understanding pH calculation for mixtures of acids
• Practicing the calculations with acid dissociation constant

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Pre-Class Quiz

Which of the following is a conjugate acid-base

pair?
A) NH4+/NH3
B) H3O+/OH–
C) H2SO3/SO32–
D) SO42-/SO32-
E) NaOH/Na+
Answer: A

•15.3
Definitions of Acids and Bases
•The Arrhenius Definition
Acid: A substance that produces H+ ions in aqueous solution
Base: A substance that produces OH– ions in aqueous solution

FIGURE 15.1 Arrhenius Acid FIGURE 15.2 Arrhenius Base

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In water, H+ ions always associate with H2O molecules to form hydronium ions
and other associated species.

:
+
H+ + H O: H O:
H H

Other associate species have the general formula H(H2O)n+.

The Brønsted–Lowry Definition

Acid: A proton (H+ ion) donor

Base: A proton acceptor

HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq)

acid base

NH3(aq) + H2O (l) HO–(aq) + NH4+(aq)

base acid

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FIGURE 15.3 •Conjugate Acid Base Pairs

Chemistry, 2Ce Copyright © 2017 Pearson Canada Inc. Slide 15-7

The Brønsted-Lowry Model of Acids and Bases

Characteristics of Acids, Bases, and Amphoteric Species

• Strong bases are strong electrolytes (e.g., NaOH).
• Weak bases are weak electrolytes (e.g., ammonia, acetate ions).
• Monoprotic acids have molecules with only one removable H+
ion (e.g., HF, HCl, HNO3, CH3COOH).
• Polyprotic acids have more than one removable H+ ion (e.g.,
H2SO4).

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The Brønsted–Lowry Definition

The Brønsted-Lowry Model of Acids and

Bases
Polyprotic Acids:
• Multiple steps of ionization, the first as a strong acid, subsequent
steps are weak.
Strong
H2SO4(aq) + H2O(ℓ) HSO4−(aq) + H3O+(aq)
Weak
HSO4−(aq) + H2O(ℓ) SO42−(aq) + H3O+(aq)

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•15.4 Acid Strength and the Acid

Ionization Constant (Ka)
HA(aq) + H2O(l) H3O+(aq) + A–(aq)

•Strong Acids
HCl (aq) + H2O (l) H3O+ (aq) + Cl–(aq)

FIGURE 15.4 Ionization of a Strong Acid FIGURE 15.5 Ionization of a Weak Acid

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HA(aq) + H2O(l) H3O+(aq) + A–(aq)

acid conjugate base

FIGURE 15.6 •Ionic Attraction and Acid Strength

Chemistry, 2Ce Copyright © 2017 Pearson Canada Inc. Slide 15-14

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The Acid Ionization Constant (Ka)

HA (aq) + H2O (l) H3O+ (aq) + A– (aq)

[H3O+][A–]
Ka =
[HA]

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•15.5 Base Solutions

•Strong Bases completely dissociate in solution

NaOH (aq) Na+ (aq) + OH– (aq)

Weak Bases
• In weak bases, only a small
fraction of molecules accept H’s
✓ weak electrolyte NH3 + H2O ⇌ NH4+ + OH−
✓ most of the weak base molecules
do not take H from water
✓ much less than 1% ionization in
water
• [HO–] << [weak base]
• Finding the pH of a weak base
solution is similar to finding the
pH of a weak acid
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Base Ionization Constant, Kb

• Base strength measured by the size of the equilibrium
constant when react with H2O
:Base + H2O ⇌ OH− + H:Base+
• The equilibrium constant is called the base ionization
constant, Kb
• larger Kb = stronger base

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FIGURE 15.7 Ionization of a Strong Base FIGURE 15.8 Ionization of a Weak Base

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Weak Bases
B(aq) + H2O(l) BH+(aq) + HO–(aq)

NH3(aq) + H2O(l) NH4+(aq) + HO–(aq)

[BH+][HO–]
Kb =
[B]

Kb (NH3) = 1.76 x 10–5

[BH+][HO–]
Kb =
[B]

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FIGURE 15.9 •Lone Pairs in Weak Bases

Chemistry, 2Ce Copyright © 2017 Pearson Canada Inc. Slide 15-23

•15.6 Autoionization of Water and pH

Water acting as both
an acid and a base

H2O(l) + H2O(l) H3O+(aq) + HO–(aq)

Acid Base
(proton donor) (proton acceptor)

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H2O(l) + H2O(l) H3O+(aq) + HO–(aq)

Ion product constant for water (Kw)

Kw = [H3O+][HO–] = 1.0 x 10–14 (at 25ºC)

In neutral solution:

[H3O+] = [HO–] = Kw = 1.0 x 10–7

Acidic Solution

[H3O+] > 1.0 x 10–7

Kw = [H3O+][HO–] = 1.0 x 10–14

[OH–] < 1.0 x 10–7

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Basic Solution

[H3O+] < 1.0 x 10–7

Kw = [H3O+][HO–] = 1.0 x 10–14

[OH–] > 1.0 x 10–7

Summarizing Kw:

Neutral Solution [H3O+] = [HO–]

Acidic Solution [H3O+] > 1.0 x 10–7

Basic Solution [OH–] > 1.0 x 10–7

In all solutions Kw = [H3O+][HO–] = 1.0 x 10–14

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Peer-Instruction 2– Determine the [H3O+] when the [OH−] = 2.5 x 10−9 M

and determine if the solution is acidic, basic, or neutral (2 min)

Given: [OH−] = 2.5 x 10−9 M

Find: [H3O+]
Conceptual
Plan: [OH−] [H3O+]

Relationships:
Solution:

Check: the units are correct; the fact that the

[H3O+] > [OH−] means the solution is acidic
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“The Power of Hydrogen”

• The weaker the acid, the lower the [A−]/[HA] ratio in
solution.
• A chemist’s shorthand way of specifying the
concentration of H3O+(aq) ions is pH.

pH = −log10[H3O+]

• Learning the relationship between pH and the

ionization constant Ka .

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The pH Scale: A Way to Quantify

Acidity and Basicity
pH = –log[H3O+]

[H3O+] = 1.0 x 10–3

pH = –log(1.0 x 10–3)

pH = 3.00

2 significant figures 2 decimal places

pH = –log(1.0 x 10–3) = 3.00

Acidic Solution Neutral Solution Basic Solution

[H3O+] = 1.0 x 10–3 [H3O+] = 1.0 x 10–7 [H3O+] = 1.0 x 10–11

pH = –log(1.0 x 10–3) pH = –log(1.0 x 10–7) pH = –log(1.0 x 10–11)

pH = 3.00 pH = 7.00 pH = 11.00

pH < 7 pH = 7 pH > 7

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pOH and Other p Scales

pOH = –log[HO–]

[HO–] = 1.0 x 10–3

pOH = –log(1.0 x 10–3)

pOH = 3.00

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Kw = [H3O+][HO–] = 1.0 x 10–14

–log (Kw) = –log ( [H3O+][HO–] ) = –log (1.0 x 10–14)

–log (Kw) = –log ([H3O+]) –log ([HO–]) = 14

pKw = pH + pOH = 14

Relative Strengths of Weak Acids and

Bases
Relationship between Ka of an Acid and Kb of Its Conjugate Base
• The stronger a weak acid is (the larger Ka is).
• For any conjugate acid-base pair
Ka × Kb = Kw
pKa + pKb = pKw (=14.00 at 25°C)
Note: Acid (base) strengths may
be compared using a logarithmic
Scale. pK a = − log10 K a
pKb = − log10 Kb
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[H3O+][A–]
HA(aq) + H2O(l) H3 O+(aq) + A–(aq) Ka (HA) =
[HA]
acid conjugate
base
[AH][HO–]
A–(aq) + H2O(l) AH(aq) + HO–(aq) Kb(B) =
[A–]
base conjugate
acid

[H3O+][A–] [HA][HO–]
Ka(AH) x Kb(A–) = = [H3O+][HO–] = Kw
[HA] [A–]

Ka × K b = Kw

Peer-Instruction 1

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Solution

Peer-Instruction 4 – Determine the [OH−] of a solution with a pH of 5.40

Given: pH = 5.40
Find: [OH−], M
Conceptual Plan:
pH [H3O+] [OH−]
Relationships:

Solution:

Check: because the pH < 7, [OH−] should be less than 1

x 10−7; and it is
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•15.7 Finding the [H3O+], [OH–],

and pH of
Acid or Base Solutions
strong or weak acid

HA (aq) + H2O (l) H3O+ (aq) + A– (aq)

autoionization of water contributes only when HA is very dilute

H2O (l) + H2O (l) H3O+ (aq) + HO– (aq)

[H3O+][A–]
Ka = Kw = [H3O+][HO–] = 1.0 x 10–14
[HA]

pKa = –log Ka

Strong Acids
The concentration of H3O+ in a strong acid solution is
simply equal to the concentration of the strong acid.

HCl (aq) + H2O (l) H3O+ (aq) + Cl– (aq)

0.1 M HCl [H3O+] = 0.1 M pH = 1.0

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Weak Acids
The concentration of H3O+ in a weak acid solution is
not equal to the concentration of the weak acid.

CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2–(aq)

0.1 M AcOH [H3O+] = 0.0013 M pH = 2.6

[H3O+][AcO–]
Ka = = 1.8 x 10–5 pKa = 4.74
[HOAc]

HA (aq) + H2O (l) H3O+ (aq) + A– (aq)

[H3O+][A–] (+x)(+x) x2
Ka = = =
[HA] (0.1–x) (0.1–x)

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[H3O+][A–] (+x)(+x) x2
Ka = = =
[HA] (0.1–x) (0.1–x)

when x << 0.1

x2 x2
Ka = ≈
(0.1–x) 0.1

[H3O+][A–] (+x)(+x) x2
Ka = = =
[HA] (0.1–x) (0.1–x)

when x is not << 0.1

(0.1)Ka – Kax = x2

x2 + Kax – (0.1)Ka = 0

–b ± b2 – 4ac
x =
2a

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Chapter 15: Acid-Base Equilibria in Aqueous Solution

Lecture 2

• Students will do practice questions to master their

understanding on acid ionization constant, base
ionization constant, autoionization of water, pH and pOH.
• Students will learn to calculate the pH of mixtures of
acids (i.e. 2 weak acids mixed, a strong acid and a weak
acid mixed).
• Students will learn to calculate the pH of polyprotic acids

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Peer-Instruction 5– What is the pH of a 0.012 M solution

of nicotinic acid, HC6H4NO2?
(Ka = 1.4 x 10−5 @ 25 °C)

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Solution:

HC6H4NO2 + H2O ⇌ C6H4NO2− + H3O+

[HA] [A−] [H3O+]

initial 0.012 0 0
change −x +x +x
equilibrium 0.012 −x x x

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Peer-Instruction 7:Find the pH of 0.100 M NH3(aq)

NH3 + H2O ⇌ NH4+ + OH−
Kb for NH3 = 1.76 x 10−5

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Kb for NH3 = 1.76 x 10−5

[NH3] [NH4+] [OH−]

initial 0.100 0 ≈0
change −x +x +x
0.100−x
equilibrium 0.100 x x

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Solution for Peer-Instruction 7

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Peer-Instruction 8

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Solution

Percent Ionization of a Weak Acid

[H3O+]equil
Percent ionization = x 100%
[HA]init

[HNO2]init = 0.500 M

[H3O+]equil = 1.7×10–2 M

1.7×10–2 M
Percent ionization = x 100% = 3.3 %
0.500 M

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▶ The equilibrium H3O+concentration of a weak acid

increases with increasing concentration of the acid.

▶ The percent ionization of a weak acid decreases with

increasing concentration of the acid.

Peer Instruction 6: What is the percent ionization

of a 2.5 M HNO2 solution?
Ka for HNO2 = 4.6 x 10−4

HNO2 + H2O ⇌ NO2− + H3O+

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Solution:
Ka for HNO2 = 4.6 x 10−4

[HNO2] [NO2−] [H3O+]

initial 2.5 0 ≈0
change −x +x +x
equilibrium 2.5−x ≈2.5 x x

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Peer-Instruction 12

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Solution

Mixtures of Acids
A Strong Acid and a Weak Acid

[HCl]init = 0.10 M and [HCO2H]init = 0.10 M

HCl(aq) + H2O(l) H3O+(aq) + Cl–(aq) Strong

HCO2H(aq) + H2O(l) H3O+(aq) + HCO2–(aq) Ka = 1.8×10–4

H2O(l) + H2O(l) H3O+(aq) + HO–(aq) Ka = 1.0×10–14

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The Strong Acid

HCl (aq) + H2O (l) H3O+ (aq) + Cl– (aq)

[HCl]init = 0.10 M therefore [H3O+]HCl = 0.10 M

The Weak Acid now Ionizes in the Presence of the Strong Acid

HCO2H (aq) + H2O (l) H3O+ (aq) + HCO2– (aq)

[H3O+][HCO2–] (0.1 + x)(+x)

Ka = 1.8 x 10–4 = =
[HA] (0.1–x)

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[H3O+][HCO2–] (0.1 + x)(+x)

Ka = 1.8 x 10–4 = =
[HA] (0.1–x)

simplify by assuming x is small compared to 0.1

(0.1)(+x)
1.8 x 10–4 ≈ =x
(0.1)

check assumption and confirm 1.8 x 10–4 << 0.1

The Autoionization of Water

H2O (l) + H2O (l) H3O+ (aq) + HO– (aq)

This can usually be ignored, but always

check assumption and confirm [H3O+] >> 10–7

Calculated pH

[H3O+]tot = [H3O+]HCl + [H3O+]HCO2H + [H3O+]H2O

= 0.10 M + 1.8 x 10–4 M = 0.1 M

pH = –log[H3O+]tot = –log(0.1) = 1.0

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Peer-Instruction 14

Solution

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Solution

Chapter 15: Acid-Base Equilibria in Aqueous Solution

Lecture 3

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• Finding the pH Of basic solutions

• Students will learn about the acid base properties of ions and salts
• Students will learn to calculate the pH of polyprotic acids

Pre-Class Quiz
Find the pH of the mixture of 0.050 M acetic acid (Ka = 1.8 x10-5) and 0.05 M
Hydrocyanic acid (Ka = 4.9 x10-10) .

Hint:

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Solution

Finding the [OH–] and pH of Basic Solutions

KOH (aq) K+ (aq) + HO– (aq)

[KOH] = 0.225 M [HO–] = 0.225 M

Kw = [H3O+][HO–] = 1.0 x 10–14

[H3O+](0.225) = 1.0 x 10–14

[H3O+] = 4.44 x 10–14

pH = –log [H3O+] = –log (4.44 x 10–14) = 13.352

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15.8 The Acid–Base Properties of Ions and Salts

HA(aq) + H2O(l) H3O+(aq) + A–(aq)

acid conjugate
base

▶ An anion that is the conjugate base of a weak acid is itself a weak base.

▶ An anion that is the conjugate base of a strong acid is pH–neutral (forms

solutions that are neither acidic nor basic).

FIGURE 15.12 Strength of

Conjugate Acid–Base Pairs

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Cations as Weak Acids

Cations That Are the Counterions of Strong Bases

are themselves pH–neutral.

KOH (aq) K+ (aq) + HO– (aq)

Cations That Are the Conjugate Acids of Weak Bases

are weak acids.

BH+(aq) + H2O(l) H3O+(aq) + B(aq)

RNH3+(aq) + H2O(l) H3O+(aq) + RNH2(aq)

acid conjugate
base

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Cations That Are Small, Highly Charged Metals

such as Al3+ and Fe3+ form weakly acidic solutions.

Al3+ (aq) + 6 H2O (l) Al(H2O)63+ (aq)

Al(H2O)63+ (aq) + H2O (l) Al(H2O)5(OH)2+ (aq) + H3O+ (aq)

Classifying Salt Solutions as Acidic, Basic, or Neutral

1. Salts in which neither the cation nor the anion acts as an acid or a base form pH–
neutral solutions.

NaCl Ca(NO3)2 KBr

Anions are conjugate bases

Cations are pH neutral
of strong acids

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2. Salts in which the cation does not act as an acid and the anion acts as a base form
basic solutions.
NaF KOOCCH3 KNO2

Cations are pH neutral Anions are conjugate bases

of weak acids

3. Salts in which the cation acts as an acid and the anion does not act as a base form
acidic solutions.

FeCl3 Al(NO3)3 NH4Br

Cations are conjugate acids Anions are conjugate

of weak bases or small, bases of strong acids.
highly charged metal ions.

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4. Salts in which the cation acts as an acid and the anion

acts as a base form solutions in which the pH depends
on the relative strengths of the acid and the base.

FeF3 Al(OOCCH3)3 NH4NO2

Cations are conjugate acids Anions are conjugate bases

of weak bases or small, of weak acids
highly charged metal ions.

SUMMARY

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•15.9 Polyprotic Acids

Sulfurous acid ionizes in two steps:

[H3O+][HSO3–]
H2SO3 (aq) + H2O (l) H3O+ (aq) + HSO3–(aq) Ka1 =
[H2SO4]
Conjugate
Acid
base = 1.6×10–2

[H3O+][SO42–]
HSO3–(aq) + H2O (l) H3O+ (aq) + SO32– (aq) Ka2 =
[HSO4–]
Acid Conjugate
base = 6.4×10–8

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Finding the pH of Polyprotic Acid Solutions

Ka1 >> Ka2 > Ka3

use Ka1 only and simplify the problem

(for dilute solutions treat Ka2 as a weak acid equilibrium)

Ka1 > Ka2

use Ka1 then treat Ka2 as a weak acid equilibrium

Sample Problem 1

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Finding the Concentration of the Anions for a Weak

Diprotic Acid Solution

H2X(aq) a+ H2O(l) H3O+(aq) + HX–(aq) Ka1

HX–(aq) + H2O(l) H3O+(aq) + X2–(aq) Ka2

suppose you want to find the concentration of X2–

Sample Problem 2

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Part 2 of the Calculation

FIGURE 15.13 •Dissociation of a Polyprotic Acid

Chemistry, 2Ce Copyright © 2017 Pearson Canada Inc. Slide 15-92

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•15.11 Lewis Acids and Bases

H H H H
+ +
H N: H O H N H O

H H H H
Lewis model focuses Brønsted–Lowry model
on the electron pair. focuses on the proton.

Lewis acid : electron pair acceptor

Lewis base : electron pair donor

H F H F
H N: F B H N : B F
H F H F

Lewis base Lewis acid adduct

A Lewis acid has an empty orbital (or can rearrange electrons to create an
empty orbital) that can accept an electron pair .

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Molecules That Act as Lewis Acids

F Cl
F B Cl Al
F Cl

incomplete octets

H Cl H Cl
H N: Cl Al H N : Al Cl
H Cl H Cl

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CH3 CH3
H2C F H2C F
:O: F B :O : B F
H2C Cl H2C F
CH3 CH3

H −
O H O
+
:O: C O C
H O H O

Water Carbon dioxide

Lewis base Lewis acid
H

O
Carbonic acid
O C
H O

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Cations That Act as Lewis Acids

3+
H + 5 H2O H
Al : O : (aq)
:O: Al3+ (aq)
(l)
H H
6

•15.11 Strengths of Acids and Bases and

Molecular Structure

•Binary Acids
+ –
H Y H + Y

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Electron Affinity of Y

Increasing electron affinity of Y

H CH3 H NH2 H OH H F

Increasing acidity

Bond Strength

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Combined Effect of Bond Strength and Polarity

FIGURE 15.14 •Acidity Trends in the Periodic Table

Chemistry, 2Ce Copyright © 2017 Pearson Canada Inc. Slide 15-103

Oxyacids
H O Y

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Organic acids are also oxyacids

:O: :O: :O:

C H C H C H
H O CH3 O H2C O

Cl
Methanoic acid Acetic acid Chloroacetic acid
Ka = 1.8×10–4 Ka = 1.8×10–5 Ka = 1.8×10–3

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Amine Bases

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