08 Chapter 16 Acid Base

GENERAL CHEMISTRY
PRINCIPLES AND MODERN APPLICATIONS

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 Simultaneous or Consecutive
Acid-Base Reactions: A General
Approach

Acids and Bases CONTENTS
16-8 Ions as Acids and Bases
16-9 Qualitative Aspects of Acid-Base

Reactions
16-10 Molecular Structure and Acid
Base Behavior
16-11 Lewis Acids and Bases

Consideration for different kinds of equilibria
general mass action law

Solubility

Large exponents do not matter, because there is
no denominator

Acid-base reactions lead only to quadratic
equations because equilibria involving
diprotic or triportic acids proceed stepwise

Be careful with large Ks

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

neglect x

Two consecutive reactions

Multiplying the K1 and K2 gives a totally wrong result!
16-1 The Arrhenius Theory: A Brief Review
H2O
HCl(g) → H+(aq) + Cl-(aq)
H2 O
NaOH(s) → Na+(aq) + OH-(aq)
Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) → H2O(l) + Na+(aq) + Cl-(aq)
H+(aq) + OH-(aq) → H2O(l)
An acid increases the H+, a base the OH- concentration in water.
Slide 19 of 51 General Chemistry: Chapter 16 Copyright © 2011 Pearson Canada Inc.

16-2 Brønsted-Lowry Theory of Acids and
Bases
An acid is a proton donor.

A base is a proton acceptor.
a c id b ase
gate g ate
n j u j u
base acid co con
NH3 + H2O NH4+ + OH-
NH4+ + OH- NH3 + H2O

acid base a se
at e b
t e a cid
o n j ug j uga
c co n
Slide 20 of 51 General Chemistry: Chapter 16 Copyright © 2011 Pearson Canada Inc.

Complex ions
FIGURE 16-11
The Lewis structure of [Al(H2O)6]3+ and a ball-and-stick representation

FIGURE 16-12
Hydrolysis of [Al(H2O)6]3+ to produce H3O+

16-9 Lewis Acids and Bases
Lewis acid
A species (atom, ion or molecule) that is an electron pair acceptor.
Lewis base
A species that is an electron pair donor.

(16.24)

Conjugate acid-base pair
CH3COOH(aq) + H2O(aq) CH3COO− (aq) + H3O+(aq) (16.2)
Acid Base Base Acid
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.

FIGURE 16-1
The ionization of CH3COOH in water

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

FIGURE 16-2
The ionization of NH3 in water

• Most acids contain at least one ionizable H atom, and many bases
contain an atom with a lone pair of electrons onto which a proton
can bind.
• For a conjugate acid–base pair, the molecular formulas for the
acid and base differ by a single proton (H+)
• When added to water, most acids protonate water molecules to
form hydronium (H3O+) ions and many bases deprotonate water
molecules to form hydroxide (OH−) ions.
FIGURE 16-3
The hydrated hydronium ion

• HCl with 12 H2O

16-2 Self-Ionization of Water and the pH Scale
2 H2O(l) H3O+ (aq) + OH−(aq) (16.3)

ion product of water
(16.4)
In pure water: (16.5)

In all aqueous solutions at 25ºC, the product of [H3O+] and [OH−] always
equals 1.0×10−14.
The self-ionization of water is partially suppressed by the addition of acid or

base to water.

pH and pOH
The “potential of the hydrogen ion” was defined in 1909 as
the negative of the logarithm of [H+].
pH = −log[H3O+]
[H3O+] = 2.5×10−3 M pH = 4.5
pH = −log(2.5×10−3) = 2.60 log [H3O+] = −4.5
[H3O+] = 10−4.5 = 3.2×10−5 M

pOH = −log[OH−]

KW = [H3O+][OH−]
−logKW = −log([H3O+] [OH−])
pKW = −log[H3O+] −log[OH−]
= pH + pOH
KW = 1.0×10−14 pKW = 14
pH + pOH = 14 (at 25ºC) (16.8)

Acidic, Basic, and Neutral Solutions

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

FIGURE 16-5
The pH scale and pH values of some common materials

16-3 Ionization of Acids and Bases in Water
FIGURE 16-6 Thymol Blue Indicator

Strong and weak acids compared pH < 1.2 < pH < 2.8 < pH

Slide 41 of 51 General Chemistry: Chapter 16 https://en.wikipedia.org/wiki/Thymol_blue.
HA(aq) + H2O(aq) A− (aq) + H3O+(aq) (16.9)
(16.10)
(16.11)

B(aq) + H2O(aq) BH+ (aq) + OH−(aq) (16.12)
(16.13)
(16.14)

HA(aq) + H2O(aq) A− (aq) + H3O+(aq)
• A strong acid or base has a large ionization constant:

Ka or Kb is much greater than 1.
• A weak acid or base has a small ionization constant:
Ka or Kb is much less than 1.
B(aq) + H2O(aq) BH+ (aq) + OH−(aq)

Lactic acid, CH3CH(OH)COOH Glycine,NH2CH2COOH

Many weak bases contain the nitrogen atom
Pyridine, C5H5N

Define the degree of ionization (α) for the ionization of an acid:
(16.15a)
For the ionization of a base:
(16.15b)
(16.16)

FIGURE 16-7
Degree of ionization in a 1M solution as a function of acid or base strength

For a weak acid or a weak base, the degree of ionization increases with
increasing dilution.
HA(aq) + H2O(aq) A− (aq) + H3O+(aq)
as V increases, must increase to maintain constant Ka.

FIGURE 16-8
Degree of ionization as a function of concentration for acids of varying strength

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

Extremly dilute
solutions:
Exercise 104

FIGURE 16-8
Degree of ionization as a function of concentration for acids of varying strength

16-4 Strong Acids and Strong Bases
HCl(aq) + H2O(aq) Cl− (aq) + H3O+(aq)
unless the solution of HCl is extremely dilute we can ignore the

self-ionization of water. Even when [HCl] is as low as 1×10−6 M,
the ionization of H2O only contributes 1%.
With strong bases, the contribution from the self-ionization of

water is also negligible.
Ca(OH)2(aq) + H2O(aq) Ca+ (aq) + 2 OH−(aq)

Strong acids
In dilute
solutions
[H3O+] of
water is
important
Strong acids

Strong bases

16-5 Weak Acids and Weak Bases
The key to solving equilibrium problems is to be able to
imagine what is going on. Ask yourself:
• Which are the principal species in solution?
• What are the chemical reactions that produce them?
• Can some reactions (for example, the self-ionization of water) be
ignored?
• Can you make any assumptions that allow you to simplify the
equilibrium calculations?
• What is a reasonable answer to the problem? For instance, should the
final solution be acidic (pH < 7) or basic (pH > 7).

More on Simplifying Assumptions
Usually treat a weak acid or weak base as though it were
essentially nonionized
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.

Weak acids

Weak acids

Weak acids

Weak acids

Weak acids

Weak acids

Weak acids

Weak acids
( )
=0

Weak acids
pH = 6.96 This is the same pH as that of 1.0 x 10-8 HCl

Phosphoric acid, H3PO4
A triprotic acid.
H3PO4 + H2O H3O+ + H2PO4−
H2PO4− + H2O H3O+ + HPO42−
HPO42− + H2O H3O+ + PO43−

Phosphoric acid, H3PO4
A triprotic acid.
H3PO4 + H2O H3O+ + H2PO4−
H2PO4− + H2O H3O+ + HPO42−
HPO42− + H2O H3O+ + PO43−

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.

(1) HPO42−(aq) + H2O(l) PO43−(aq) + H3O+(aq) Ka(HPO42−)=?
(2) HPO42−(aq) + H2O(l) H2PO4−(aq) + OH−(aq) Kb(HPO42−)=?
Ka(HPO42−) = Ka3(H3PO4) = 4.2×10−13
The HPO42− ion exhibits a greater tendency to react with water

as a base than as an acid
Kb(PO43-) = 1.0 x 10-14 / 4.2 x 10-13 = 0.24
The phosphate ion is a strong base, 13000 time stronger than ammonia
with Kb =1.8 x 10-5.
A Somewhat Different Case: H2SO4
Sulfuric acid, H2SO4
A diprotic acid.
H2SO4 + H2O H3O+ + HSO4− Ka = very large
HSO4− + H2O H3O+ + SO42− Ka = 1.1×10−2
the small second ionization can be treated as in EXAMPLE 16-11

16-8 Ions as Acids and Bases
NH4+ + H2O NH3 + H3O+ (16.17)

Acid (1) Base (2) Base (1) Acid (2)
CH3CO2− + H2O CH3CO2H + OH− (16.18)

Base (2) Acid (1) Acid (2) Base (1)
[NH3] [H3O+]
Ka= =? (16.19)
[NH4+]
[NH3] [H3O+]
NH + H2O 4
+
NH3 + H3O +
Ka= =?
Acid (1) Base (2) Base (1) Acid (2) [NH4 ] +
CH3CO2− + H2O CH3CO2H + OH−

Base (2) Acid (1) Acid (2) Base (1)
[NH
[NH33]][H
[H33O
O++]] [OH
[OH-]−] KW 1.0×10−14
Ka= = = = 5.6×10−10
[NH
[NH44++]] [OH
[OH-−]] Kb 1.8×10−5
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
CH3CO2− + H2O CH3CO2H + OH− (16.18)
The conjugate of weak is weak.
The conjugate of strong is extremely weak.
2
Hydrolysis
Water (hydro) causing cleavage (lysis) of a bond.
Na+ + H2O → Na+ + H2O No reaction
Cl− + H2O → Cl− + H2O No reaction
NH4+ + H2O → NH3 + H3O+ Hydrolysis
Ammonium ion hydrolyzes (and chloride ion does not).
The pH of Salt Solutions
• Metal ions with a +1 or +2 charge usually do not affect the pH

of a solution. Metal ions with higher charges may
(for example Al3+, Fe3+, Cr3+, see Slide 16 - 72)
• Some polyatomc cations act as acids in water. Important
examples are NH4+ and the protonated forms of amines.
• Many anions act as bases in water. It is helpful to think about
the acid strength of the conjugate acid, HA.
16-9 Qualitative Aspects of Acid-Base
Reactions
HA + B A− + BH+ (16.21)
Acid Base Base Acid
For an acid-base reaction, equilibrium favors the formation of the weaker acid
and the weaker base.
HA(aq) + B(aq) A− (aq) + BH+ (aq)
with
(16.22)
Kb(B) = Kw / Ka(BH+) or Ka(HA) = Kw / Kb(A-)
For an acid-base reaction, equilibrium favors the formation of the weaker acid
and the weaker base.
CH3COOH + C5 H5 N 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
If the acid or base in an acid-base reaction is strong, they react essentially to
completion.
16-10 Molecular Structure and Acid-Base
Behavior
Why is HCl a strong acid, but HF is a weak one?

Why is CH3CO2H a stronger acid than CH3CH2OH?
Molecular structure and acid strength are related.
Strengths of Binary Acids
HX(g) H+(g) + X−(g) (16.23)
FIGURE 16-10
Bond dissociation energies (kJ mol−1) and Ka values for some binary acids
When comparing binary acids of elements in the same row of the periodic table,
acid strength increases as the polarity of the bond increases.
When comparing binary acids of elements in the same group of the periodic
table, acid strength increases as the length of the bond increases.
HF is even weaker than expected based on periodic trends.
HF + H2O (F−···H3O+) H3O+ + F−

Ion pair
Strengths of Oxoacids
Factors promoting electron withdrawal from the OH bond to

the oxygen atom:
High electronegativity (EN) of the central atom.
A large number of terminal O atoms in the molecule.
H−O−Cl H−O−Br
ENCl = 3.0 ENBr= 2.8
Ka = 2.9×10−8 Ka = 2.1×10−9
·· − ·· −
O O
··
··
··
··
·· 2+ ·· ·· + ··
H O S O H H O S O H
·· ·· ·· ·· ··
−
O
··
··
··
Ka ≈103 Ka =1.3×10−2
Strengths of Organic Acids
H O H H
··
··
·· ··
H C C O H H C C O H
·· ··
H H H
Acetic acid Ethanol

Ka = 1.8×10−5 Ka =1.3×10−16
Focus on the anions formed in the ionization.
Ethoxide ion
H H
·· −
H C C O
··
··
H H
Acetate ion
H O
·· −
··
H O
··
··
··
H C C H C C
O·−
··
H O
··
· H
··
··
Chain length has little effect on the acid strength.
H O
··
acetic acid
··
H C C Ka = 1.8×10−5
O·−
··
H · octanoic acid
··
Ka = 1.3×10−5
H H H H H H H O
··
··
H C C C C C C C C
O·−
··
H H H H H H H ·
Slide 16 - 136 General Chemistry: Chapter 16 ·· Copyright © 2017 Pearson Canada Inc.
Substitution may strongly affect acid strength.
H O
··
acetic acid
··
H C C Ka = 1.8×10−5
chloroacetic acid
O·−
··
H ·· ·
Ka = 1.4×10−3
Cl O
··
··
H C C
O·−
··
H ·
··
Strengths of Amines as Bases
H H
H N Br N
··
··
H H
ammonia bromamine
NH3, pKb = 4.74 NH2Br, pKb = 7.61
H H H H
H N H C NH2 H C C NH2
··
H H H H
ammonia methylamine ethylamine
NH3, pKb = 4.74 CH3NH3, pKb = 3.38 CH3CH2NH3, pKb = 3.37
Rationalization of Acid Strengths: An
Alternative Approach
Two approaches to rationalize the strength of an acid, HA.
• factors that cause electron density to be drawn away from the H atom
• factors that make A− stable with respect to protonation
• the more electronegative the atom is, the better it is able to
bear a negative charge. (CH3O− is more stable than NH2−)
• the larger the atom, the greater its ability to bear a negative
charge. (HS− is more stable than HO−)
• the stability of the anion increases as the number of
electron-withdrawing groups increases.
• the stability of the anion increases as the number of atoms
sharing the charge increases
ionic charge
ρ = charge density =
ionic volume
End of Chapter
16-7 Simultaneous or Consecutive Acid-Base
Reactions: A General Approach
1. Identify species present in solution (excluding H2O).

2. Write equations that include these species.
Number of equations = number of unknowns.
a) equilibrium constant expressions.
b) material balance equations.
c) electroneutrality condition.
3. Solve the system of equations for the unknowns.
Consider 0.10 M H3PO4
Species in solution
H3PO4, H2PO4−, HPO42−, PO4 3−, H3O+, OH−
Reactions and equilibrium constants
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4−(aq)
H2PO4−(aq) + H2O(l) H3O+(aq) + HPO42−(aq)
HPO42−(aq) + H2O(l) H3O+(aq) + PO43−(aq)
2 H2O(l) H3O+(aq) + OH−(aq)
Consider 0.10 M H3PO4
Species in solution
H3PO4, H2PO4−, HPO42−, PO4 3−, H3O+, OH−
Reactions and equilibrium constants
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4−(aq)
H2PO4−(aq) + H2O(l) H3O+(aq) + HPO42−(aq)
HPO42−(aq) + H2O(l) H3O+(aq) + PO43−(aq)
2 H2O(l) H3O+(aq) + OH−(aq)
We have four equations and six unknowns. Need two equations.
Material balance equation (MBE)
0.1 M = [H3PO4] + [H2PO4−] + [HPO42−] + [PO4 3−]
Charge balance equation (CBE)
[H3O+] = [H2PO4−] + 2 × [HPO42−] + 3 × [PO4 3−] + [OH−]
In principle, the system of six equations can be used to solve

for six unknowns, either by making appropriate simplifying
approximations or by computerized calculation.

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GENERAL CHEMISTRY

PRINCIPLES AND MODERN APPLICATIONS

PETRUCCI HERRING MADURA BISSONNETTE

Acids and Bases 16

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

16-1 Acids, Bases, and Conjugate

16-3 Ionization of Acids and Bases in

16-4 Strong Acids and Strong Bases

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

16-8 Ions as Acids and Bases

16-9 Qualitative Aspects of Acid-Base

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

general mass action law

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

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

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

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

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

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

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

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

Na+(aq) + OH-(aq) + H+(aq) + Cl-(aq) → H2O(l) + Na+(aq) + Cl-(aq)

H+(aq) + OH-(aq) → H2O(l)

An acid increases the H+, a base the OH- concentration in water.

Slide 19 of 51 General Chemistry: Chapter 16 Copyright © 2011 Pearson Canada Inc.

An acid is a proton donor.

NH4+ + OH- NH3 + H2O

Slide 20 of 51 General Chemistry: Chapter 16 Copyright © 2011 Pearson Canada Inc.

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

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

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

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

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

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

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

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

Base Acid Acid Base

Conjugate acid-base pair

Slide 16 - 27 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

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

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

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

2 H2O(l) H3O+ (aq) + OH−(aq) (16.3)

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

In pure water: (16.5)

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

The self-ionization of water is partially suppressed by the addition of acid or

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

[H3O+] = 2.5×10−3 M pH = 4.5

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

[H3O+] = 10−4.5 = 3.2×10−5 M

Slide 16 - 34 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

Slide 16 - 35 General Chemistry: Chapter 16 Copyright © 2017 Pearson Canada Inc.

−logKW = −log([H3O+] [OH−])

pKW = −log[H3O+] −log[OH−]

pH + pOH = 14 (at 25ºC) (16.8)