Chapter 4:

ACIDS AND BASES

prepared by Nur Hikamah Seth

1
 SUBTOPICS
4.1: Definition: Arrhenius, Bronsted Lowry & Lewis

4.2: Strength of Acids & Bases

• pH & pOH
• Strong acid & Base
• Degree of Dissociation
• Kw, Ka, Kb, pKa, pKb

4.3: Hydrolysis
4.4:Common Ion Effect
Buffer
• Definition
• Henderson-Hesselbalch Equation
• Functions of buffer solution

4.5: Acid-base Titration Curve & Indicators

N.H.Seth 2
4.1: DEFINITION:
ARRHENIUS,
BRONSTED
LOWRY & LEWIS

N.H.Seth 3
 GUIDING QUESTIONS

What is an acid?

What is a base?

4
 INTRODUCTION:
General Properties of Acids & Bases
Acid and bases form a large group of
chemicals with characteristic properties

Acids Bases

Taste sour Taste bitter & slippery feel

Change color of wet litmus Change color of wet litmus

paper to red (pH < 7) paper to blue (pH > 7)

React with metals Do not react with metals

N.H.Seth 5
 Acids

• Exhibit acidic properties in the presence of water –

form H3O+ ions (hydronium ion)
• React with base - form salt and water
HCl + NaOH → NaCl + H2O
• React with metals, - produce H2 gas
2 HCl + Na → 2 NaCl + H2
• React with carbonates – liberate CO2 gas
HCl + Na2CO3 → 2 NaCl + H2O + CO2

N.H.Seth 6
 Example of common acids
Name of acid Formula Uses
Detergents,
Sulfuric Acid H2SO4
pharmaceuticals
Nitric Acid HNO3 Fertilizers

Phosphoric Acid H3PO4 Rust remover

Brick and ceramic
Hydrochloric acid HCl
tile cleaner
Flavoring,
Acetic Acid CH3COOH
preservative
Carbonic Acid H2CO3 Carbonated drinks
N.H.Seth 7
 Bases
• Bases exhibit their basic properties only in the presence
of water due to the OH- ions

• React with an acid to form a salt and water

2 NaOH + H2SO4 → Na2SO4 + 2 H2O

N.H.Seth 8
 Example of common bases
Name of bases Formula Uses
Oven and drain
Sodium hydroxide NaOH
cleaners
Potassium
KOH liquid soap
hydroxide
Magnesium “MOM” Milk of
Mg(OH)2
hydroxide magnesia
stabilizer for
Barium hydroxide Ba(OH) 2
plastics

Ammonia NH3 Household cleaner

N.H.Seth 9
Definitions of Acid & Base

Bronsted
Arrhenius
-Lowry

Lewis

N.H.Seth 10
 Arrhenius Theory
Presented by Svante Augustus Arrhenius in 1884.

Acids Bases

Substances that contain

Substances that contain the
hydrogen and produces
hydroxyl group and produce
H+ ions in aqueous
OH- ions in aqueous solutions
solutions.

Example: Example:
HCl, HNO3 and H2SO4 NaOH and Ca(OH)2
N.H.Seth 11
 Arrhenius Theory

HCl ionizes in water, NaOH dissociates in water,

producing H+ and Cl– producing Na+ and OH–
ions ions
N.H.Seth 12
HCl + H2O → H3O+ + Cl-
Arrhenius
H2O ACIDS
HNO3 H+ + NO3-
H2O
H2SO4 2 H+ +
SO42-

H2O
NaOH Na+ + OH- Arrhenius
H2O BASES
Ca(OH)2 Ca2+ + 2 OH-

N.H.Seth 13
 Limitation !!!
• Arrhenius theory for acids and bases are limited to:
• Compounds containing H and OH respectively.
• Only applicable to aqueous solutions.

Does not explain why molecular substances, such as NH3,

dissolve in water to form basic solutions – even though they do
not contain OH– ions
Does not explain how some ionic compounds, such as Na2CO3
or Na2O, dissolve in water to form basic solutions – even though
they do not contain OH– ions
Does not explain why molecular substances, such as CO2,
dissolve in water to form acidic solutions – even though they do
not contain H+ ions.
N.H.Seth 14
 Bronsted-Lowry Theory
Proposed by Johannes Bronsted and Thomas M.Lowry
in 1923

ACIDS BASES

Proton (H+) donor: Proton (H+) acceptor:

Any substance that can Any substance that can
donate a proton to accept a proton from another
another substance substance

N.H.Seth 15
 Bronsted Acids & Bases
Example 1:
NH4+(aq) + H2O(l) ↔ NH3(aq) + H3O+(aq)
(acid) (base)
In forward reaction: NH4+ donates a proton to H2O while
In reverse reaction : H3O+ donates a proton to NH3.
Both NH4+ and H3O+ are Bronsted acids.
Example 2:
CO32-(aq) + H2O(l) ↔ HCO3- (aq) + OH-(aq)
(base) (acid)
In forward reaction: CO32- accepts a proton from H2O while
In reverse reaction : OH- accepts a proton from HCO3-.
Both CO32- and OH- are Bronsted bases.

N.H.Seth 16
 Brønsted-Lowry Acid-Base
Reactions
• One of the advantages of Brønsted-Lowry theory is that
it allows reactions to be reversible
H–A + :B ⇔ :A– + H–B+
• The original base has an extra H+ after the reaction, so
it will act as an acid in the reverse process

• And the original acid has a lone pair of electrons after

the reaction – so it will act as a base in the reverse
process
H–A + :B ⇔ :A– + H–B+

N.H.Seth 17
❖ In connection with the Bronsted-Lowry model,
there are some terms that are used frequently:-

1. Conjugate base
2. Conjugate acid

N.H.Seth 18
 Conjugate Base Conjugate Acid

• The species formed when • The species formed when

a proton is removed from a proton is added to a base
an acid • Accepts a proton
• An acid become its
conjugate base when it
donates proton

Conjugate acid-base pairs are chemical species

whose formulae differ only by one proton, H+.

N.H.Seth 19
❖ Example of Bronsted-Lowry acid in water solvent
❖ Hence, water acts as Bronsted-Lowry base

Acid Conjugate
base

HA + H2O ⮀ A- + H3O+

Conjugate
Base
acid
N.H.Seth 20
❖ Example of Bronsted-Lowry base such as ammonia
accepts a proton from the solvent (water), acts as
Bronsted Lowry acid

Conjugate
Base
acid

NH3 + H2O ⮀ NH4+ + OH-

Conjugate
Acid
base
N.H.Seth 21
The Conjugate Pairs in Some Acid-Base Reactions

Conjugate Pair

Acid + Base Base + Acid

Conjugate Pair

Reaction 1 HF + H2O F- + H3O+

Reaction 2 HCOOH + CN- HCOO- + HCN

Reaction 3 NH4+ + CO32- NH3 + HCO3-

Reaction 4 H2PO4- + OH- HPO42- + H2O

Reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+

Reaction 6 HPO42- + SO32- PO43- + HSO3-

N.H.Seth 22
 Amphoteric Substances
• Amphoteric substances can act as either an acid or a
base
– because they have both a transferable H and an atom with
lone pair electrons
• Water acts as base, accepting H+ from HCl
HCl(aq) + H2O(l) → Cl–(aq) + H3O+(aq)
• Water acts as acid, donating H+ to NH3
NH3(aq) + H2O(l) ⇔ NH4+(aq) + OH–(aq)
Therefore, water is amphoteric

N.H.Seth 23
 Limitation !!!
• Limited to compounds with ionisable H atoms
only.
• Example:
• NaOH is an Arrhenius base but it is not a
Bronsted-Lowry base because it does not
accept a proton.

NaOH(s) + H + no reaction

N.H.Seth 24
Example 4.1.1

Identify acid-conjugate base pairs in the reaction

H3O+ (aq) + Cl- (aq) → HCl (g) + H2O(l)

Acid Base Conjugate Conjugate

acid base

N.H.Seth 25
Example 4.1.2

❖ Write a reaction that shows that HCO3- is a Brønsted

acid when reacted with OH-

HCO3-(aq) + OH-(aq) ↔ H2O(l) + CO32-(aq)

❖ Write a reaction that shows that HCO3- is a Brønsted

base when reacted with H3O+(aq)

HCO3-(aq) + H3O+(aq) ↔ H CO
2 3(aq) + H2O(l)

N.H.Seth 26
 Lewis Theory
❖ A wider definition of acids and bases was stated
by G.N.Lewis in 1938

❖ Highlights the role of the electron pair

Acids Bases
Acids are defined as Bases are defined as
electron pair acceptors. electron pair donors.
Electron deficient, Electron rich, therefore
therefore electrophile nucleophile

N.H.Seth 27
Example of Lewis acid-base:
ionization of ammonia
electron
transfer

Lewis Lewis
base acid

N.H.Seth 28
Examples of Lewis Acid–Base Reactions

N.H.Seth 29
Examples of Lewis Acid–Base Reactions

Ag+(aq) + 2 :NH3(aq) → Ag(NH3)2+(aq)

Lewis Lewis
Adduct
Acid Base

N.H.Seth 30
Examples of Lewis acid:
❖ Positively charged ions (e.g. Al3+, Cr3+)
❖ Central atom incomplete octet (Boron in BF3)

Examples of Lewis base:

❖ Negatively charged ions (CN-, OH-)
❖ Central atom has lone pair electrons (oxygen in H2O)
❖ Anions are better Lewis Bases than neutral atoms or
molecules (N: < N:−)
❖ Generally, the more electronegative an atom, the less
willing it is to be a Lewis Base (O: < S: )

N.H.Seth 31
Example 4.1.3

Identify the Lewis acids and Lewis bases in the

following reactions:
donor
(a) H+ + OH- H2O
H+ - acid; OH- - base
acceptor

donor
-
(b) Cl + BCl3 BCl4- BCl3 - acid; Cl- - base
acceptor

donor
(c) K+ + 6H2O K(H2O)6+
K+ - acid; 6H2O - base
acceptor
N.H.Seth 32
 Practice 4.1.1:

1.Identify the Lewis Acid and Lewis Base in Each Reaction

Lewis
Base Lewis
Acid

Lewis Lewis
Base Acid

N.H.Seth 33
Tro, Chemistry: A Molecular Approach, 2/e
Practice 4.1.1:

2. Which of the following does not fit the definition of a

Brønsted Base?
A) CO32– B) NH3 C) H2O D) NH4+ E) HCO3–

3. In the reaction HSO4–(aq) + OH–(aq) SO42–(aq) + H2O(l),

the conjugate acid-base pairs are

N.H.Seth 34
4. 2 STRENGTH OF
ACIDS AND BASES

N.H.Seth 35
 The Ion Product of Water,
Constant for Water, Kw
[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]

At 25°C: Kc[H2O] = Kw = [H+][OH-] =1.0 x 10-14

The ion-product constant (Kw) is the product of the molar concentrations of

H+ and OH- ions at a particular temperature.

In pure water,
[H3O+] = [OH-] = = 1.0x10-7 (at 25°C)

Both ions are present Solution Is

in all aqueous system
Based on the autonization of
equilibrium of water, an increase [H+] = [OH-] neutral
[H+] causes a decrese in [OH-] and
[H+] > [OH-] acidic
vice versa, in order that the Kw
remains unchanged. [H+] < [OH-] basic
N.H.Seth 36
Figure 4.2 The relationship between [H3O+] and [OH-] and the
relative acidity of solutions.

N.H.Seth 37
 Example 4.2.1

The concentration of OH- ions in a certain household ammonia

cleaning solution is 0.0025 M. Calculate the concentration of
H+ ions.

Strategy

We are given the concentration of the OH- ions and asked to

calculate [H+]. The relationship between [H+] and [OH-] in water
or an aqueous solution is given by the ion-product of water, Kw
[Equation (15.3)].

38
 Example 4.2.1
Solution

Rearranging Equation (15.3), we write

Check

Because [H+] < [OH-], the solution is basic, as we would expect

from the earlier discussion of the reaction of ammonia with
water.

39
 pH
❖ pH is a measure of the concentration of H+ or H3O+
ions in a solution.

pH = -log [H+] or pH = -log [H3O+]

❖ The unit is molarity, M (mol dm-3).

❖ The numerical values of pH are inversely

propotional to the [H3O+];
- the value of pH increases as the [H3O+]
decreases.

N.H.Seth 40
 pOH
❖ pOH is measure of the concentration of OH- ions
in a solution.

pOH = -log [OH-]

❖ Unit of [OH-] is molarity, M (mol dm-3).

The pH and pOH of an aqueous solution is related by

the equation:
pH + pOH = 14
N.H.Seth 41
 pOH = -log [OH-]

[H+][OH-] = Kw = 1.0 x 10-14

-log [H+] – log [OH-] = 14.00

pH + pOH = 14.00

N.H.Seth pH Meter 42
pH scale
N.H.Seth 43
Methods for measuring the pH of an
aqueous solution

pH (indicator) pH meter
paper

N.H.Seth
Example 4.2.2 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In an art restoration project, a conservator prepares

copper-plate etching solutions by diluting concentrated
HNO3 to 2.0 M, 0.30 M, and 0.0063 M HNO3. Calculate
[H3O+], pH, [OH-], and pOH of the three solutions at 25°C.

PLAN: HNO3 is a strong acid so it dissociates completely, and [H3O+]

= [HNO3]init. We use the given concentrations and the value
of Kw at 25°C to find [H3O+] and [OH-]. We can then calculate
pH and pOH.
SOLUTION:
Calculating the values for 2.0 M HNO3:
[H3O+] = 2.0 M pH = -log[H3O+] = -log(2.0) = -0.30
Kw 1.0x10-14
[OH-] = = = 5.0x10 -15 M
[H3O+] 2.0
pOH = -log[OH-] = -log(5.0x10-15) = 14.30
N.H.Seth 45
Example 4.2.2

Calculating the values for 0.30 M HNO3:

[H3O+] = 0.30 M pH = -log[H3O+] = -log(0.30) = 0.52
Kw 1.0x10-14 -14 M
[OH-] = = = 3.3x10
[H3O+] 0.30
pOH = -log[OH-] = -log(3.3x10-14) = 13.48

Calculating the values for 0.0063 M HNO3:

[H3O+] = 0.0063 M pH = -log[H3O+] = -log(0.30) = 2.20
Kw 1.0x10-14 -12 M
[OH-] = = = 1.6x10
[H3O+] 0.0063
pOH = -log[OH-] = -log(1.6x10-12) = 11.80

N.H.Seth 46
Practise 4.2

1. 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.
(ans: 1.5 x 10-5 M)

2. In a NaOH solution [OH-] is 2.9 x 10-4 M. Calculate the pH of the

solution. (ans: 10.46)

3. In an art restoration project, a conservator prepares copper-plate

etching solutions by diluting concentrated HNO3 to 0.0063M HNO3.
Calculate [H3O+], pH, [OH-], and pOH of the solutions at 250C.

4. What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution? (ans: 12.6)

N.H.Seth 47
Strength of Acids & Bases

The strength of an acid or base depends

on the degree of dissociation of the acid
or base in water

N.H.Seth 48
 Strong and Weak Acid
STRONG ACID WEAK ACID

dissociates completely dissociates partially

produce high conc. of H+ ions produce low conc. of H+ ions

Example:
Example:
HCl, HBr, HI, HNO3, H2SO4,
HF, H3PO4, CH3COOH
HClO3, HClO4

N.H.Seth 49
 Complete dissociation of
strong acid

Strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

N.H.Seth 50
 Incomplete dissociation of
weak acid

Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)

N.H.Seth 51
❖ The strength of an acids depends on its ability to
donate protons.
▪ The stronger of the acid, the greater its tendency to
donate a proton to the base.

❖ The stronger the acid, the weaker its conjugate base.

❖ The weaker the acid, the stronger its conjugate base.

N.H.Seth 52
N.H.Seth 53
 Weak Acids (HA) and
Acid Ionization Constants, Ka
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

HA (aq) H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]

Ka is the acid ionization constant

weak acid
Ka
strength

N.H.Seth 54
Ionization Constant of a Weak
Acid (Ka)
❖ Chemical equation when a weak acid dissolves in
water:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)

❖ Equilibrium constant, Kc :
[H3O+][A-]
Kc =
[H2O][HA]

NOTE: concentration of water is virtually constant.

N.H.Seth 55
 [H3O+][A-]
Kc [H2O] = Ka =
[HA]

Ka is ionization constant of weak acid

❖ The values of Ka:

▪ Influenced only by the changes in temperature.
Usually stated at a 25 °C
▪ The stronger the acid, the greater the extent of
dissociation and larger the value of Ka.

N.H.Seth 56
❖ Since the values of Ka are very small, it is more
convenient to use the values of pKa to compare
the strength of acids:
▪ The larger the value of pKa, the smaller the value
of Ka and the weaker the acid.

pKa = -log Ka

N.H.Seth 57
The Relationship Between Ka and pKa

Acid Name (Formula) Ka at 250C pKa

Hydrogen sulfate ion (HSO4-) 1.02x10-2 1.991

7.1x10-4 3.15

acid strength
Nitrous acid (HNO2)
Acetic acid (CH3COOH) 1.8x10-5 4.74

Hypobromous acid (HBrO) 2.3x10-9 8.64

Phenol (C6H5OH) 1.0x10-10 10.00

N.H.Seth 58
N.H.Seth 59
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.

N.H.Seth 60
Example 4.2.3
The pH of a 0.10 M solution of formic acid (HCOOH) is 2.39. What is
the Ka of the acid?

Strategy Formic acid is a weak acid. It only partially ionizes in water.

Note that the concentration of formic acid refers to the initial
concentration, before ionization has started. The pH of the solution,
on the other hand, refers to the equilibrium state. To calculate Ka,
then, we need to know the concentrations of all three species: [H +],
[HCOO-], and [HCOOH] at equilibrium. As usual, we ignore the
ionization of water. The following sketch summarizes the situation.

61 N.H.Seth
Example 4.2.3
Solution We proceed as follows.

Step 1: The major species in solution are HCOOH, H+, and the
conjugate base HCOO-.

Step 2: First we need to calculate the hydrogen ion

concentration from the pH value

pH = -log [H+]
2.39 = -log [H+]

Taking the antilog of both sides, we get

[H+] = 10-2.39 = 4.1 x 10-3 M

62 N.H.Seth
Example 4.2.3
Next we summarize the changes:

HCOOH(aq) H+(aq) + HCOO-(aq)

Initial (M): 0.10 0.00 0.00
Change (M): - 4.1 x 10-3 +4.1 x 10-3 + 4.1 x 10-3
Equilibrium (M): (0.10 - 4.1 x 10-3) 4.1 x 10-3 4.1 x 10-3

Note that because the pH and hence the H+ ion concentration is known, it follows
that we also know the concentrations of HCOOH and HCOO- at equilibrium.

63 N.H.Seth
Example 4.2.3
Step 3: The ionization constant of formic acid is given by

Check
The Ka value differs slightly from the one listed in Table 15.3 because of the
rounding-off procedure we used in the calculation.

64 N.H.Seth
 Strong and Weak Base
STRONG BASE WEAK BASE

dissociates completely dissociates partially

produce high conc. of OH-

produce low conc. of OH- ions
ions

Example:
NaOH, KOH, Ca(OH)2,
Sr(OH)2, Ba(OH)2 Example:
NH3, CH3NH2, C2H5NH2
(hydroxides of the Group I
and Group II metals)
N.H.Seth 65
❖ Strong bases dissociate completely to form OH-
ions in aqueous solutions.

H2
NaOH (s) O Na+ (aq) + OH- (aq)
H2 + (aq) + OH- (aq)
KOH (s) O K

❖ Weak bases do not dissociate completely to

form OH- ions in aqueous solutions.

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

N.H.Seth 66
 Weak Bases and
Base Ionization Constants, Kb
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

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

weak base
Kb
strength
Solve weak base problems like weak acids except solve
for [OH-] instead of [H+].
N.H.Seth 67
N.H.Seth 68
❖ The strength of a base can also be measured in terms
of pKb.
▪ The smaller the value of pKb, the stronger is the
base.

pKb = -log Kb

N.H.Seth 69
 Degree of dissociation, α
Ionized acid concentration at equilibrium x 100%
percent ionization =
Initial concentration of acid
For a monoprotic acid HA,
[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

The degree of dissociation, α of acid HA and base BOH is expressed

respectively as [H+] [OH-]
α= α=
[HA]0 [BOH]0
The degree of dissociation of an acid or a base varies with concentration
but the ionization/dissociation constant Ka or Kb remain unchanged as the
concentration of the acid and base varies at same temperature
N.H.Seth 70
 Relationship between Ka and Kb for a
Conjugate Acid-Base Pair
HA + H2O H3O+ + A-
A- + H2O HA + OH-

2H2O H3O+ + OH-

Kc for the overall equation = K1 x K2, so

[H3O+][A-] x [HA][OH-] = [H3O+][OH-]

[HA] [A-]
Ka x Kb = Kw

This relationship is true for any conjugate acid-base pair.

N.H.Seth 71
Relationship Between Ka, Kb and Kw
Ka x Kb = Kw = 10-14
Acid conjugate base

Kb x Ka = Kw = 10-14
Base conjugate acid

Relationship Between pKa, pKb and pKw

pKa + pKb = pKw = 14
acid conjugate base

pKb + pKa = pKw = 14

base conjugate acid
N.H.Seth 72
Example 4.2.4 Determining the pH of a Solution of A-

PROBLEM: Sodium acetate (CH3COONa, or NaAc for this problem)

has applications in photographic development and textile
dyeing. What is the pH of 0.25 M NaAc? Ka of acetic
acid (HAc) is 1.8x10-5.

PLAN: Sodium salts are soluble in water and acetate is the anion of
HAc so it acts as a weak base. We write the base dissociation
equation and the expression for Kb, and solve for [OH-]. We
recall that any soluble ionic salt dissociates completely in
solution, so [Ac-]init = 0.25 M.

SOLUTION: Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)

[HAc][OH-]
Kb =
[Ac-]

N.H.Seth 73
Example 4.2.4
Concentration (M) Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)
Initial 0.25 - 0 0
Change -x - +x +x
Equilibrium 0.25 - x - x x

Kw 1.0x10-14
Kb = = = 5.6x10 -10 M
Ka 1.8x10-5

[HAc][OH-] x2
Kb = 5.6x10-10 = ≈ so x = [OH-] = 1.2x10-5 M
-
[Ac ] 0.25

Checking the assumption:

0.25 M = 139 x102 (>100%; assumption is justified)

1.8x10-5

N.H.Seth 74
Example 4.2.4
K 1.0x10 -14
w
[H3O+] = = = 8.3x10-10 M
[OH-] 1.2x10-5

pH = -log (8.3x10-10) = 9.08

N.H.Seth 75
Example 4.2.5
Calculate the pH of a 0.5 M HF solution (at 250C).

[H+][F-]
Ka = = 7.1 x 10-4
[HF]

HF (aq) H+ (aq) + F- (aq)

I 0.50 0.00 0.00

C -x +x +x
E 0.50 - x x x

N.H.Seth 76
Example 4.2.5
x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 – x ≈ 0.50
0.50 - x

x2
Ka ≈ = 7.1 x 10-4 x2 = 3.55 x 10-4
0.50
x = 0.019

[H+] = [F-] = 0.019 M

[HF] = 0.50 – x = 0.48 M

pH = -log [H+] = 1.72

N.H.Seth 77
 Example 4.2.6: Find the pH of 0.100 M NH3(aq)

Kb for NH3 = 1.76 x 10−5

determine the value of
Kb from Table 15.8 [NH3] [NH4+] [OH−]
because Kb is very initial 0.100 0 ≈0
small, approximate the
[NH3]eq = [NH3]init and
change −x +x +x
solve for x equilibrium 0.100−x
0.100 x x

0.1M = 555 x102 (>100%; assumption is justified)

N.H.Seth 78
1.8x10-5
Example 4.2.6:

⮚To find pH of 0.100 M NH3(aq)

From previous calculation, obtained:

x = 1.33 x 10−3

N.H.Seth 79
 4.3 HYDROLYSIS
Definition: Decomposition Of A Chemical Compound By
Reaction With Water. (Reaction with water)

N.H.Seth 80
 Acid-Base Properties of Salts
Salts are water-soluble ionic compounds
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal ion
(except Be2+) and the conjugate base of a strong acid
(e.g. Cl-, Br-, and NO3-).
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Basic Solutions:
Salts derived from a strong base and a weak acid.
CH3COONa (s) H2O Na+ (aq) + CH3COO- (aq)

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

N.H.Seth 81
 Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.

H2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

2+

N.H.Seth 82
 Acid-Base Properties of Salts

Solutions in which both the cation and the anion hydrolyze:

• Kb for the anion > Ka for the cation, solution will be basic
• Kb for the anion < Ka for the cation, solution will be acidic
• Kb for the anion ≈ Ka for the cation, solution will be neutral

N.H.Seth 83
 Salts of Weakly Acidic
Cations and Weakly Basic
Anions
If a salt that consists of the anion of a weak acid and the
cation of a weak base, the pH of the solution will
depend on the relative acid strength or base strength of
the ions.
NH4CN

NH4+ is the cation of a CN- is the anion of a

weak base, NH3. weak acid, HCN.

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

CN-(aq) + H2O(l) HCN(aq) + OH-(aq)

N.H.Seth 84
The reaction that proceeds farther to the right determines the
pH of the solution, so we need to compare the Ka of NH4+
with the Kb of CN-.

K 1.0x10-14
Ka of NH4 + = w
= = 5.7x10-10
Kb of NH3 1.76x10-5

K 1.0x10-14
Kb of CN- = w
= = 1.6x10-5
Ka of HCN 6.2x10-10

Since Kb of CN- > Ka of NH4+, CN- is a stronger base than

NH4+ is an acid. A solution of NH4CN will be basic.

N.H.Seth 85
N.H.Seth 86
 Example 4.3.1
Predict whether the following solutions will be acidic, basic, or
nearly neutral:

(a)NH4I

(b) NaNO2

(c) NH4F

87 N.H.Seth
 Example 4.3.1
Strategy

In deciding whether a salt will undergo hydrolysis, ask yourself

the following questions: Is the cation a highly charged metal ion
or an ammonium ion? Is the anion the conjugate base of a
weak acid? If yes to either question, then hydrolysis will occur.
In cases where both the cation and the anion react with water,
the pH of the solution will depend on the relative magnitudes of
Ka for the cation and Kb for the anion (see Table 15.7).

88 N.H.Seth
Example 4.3.1
Solution
We first break up the salt into its cation and anion components
and then examine the possible reaction of each ion with water.
(a)The cation is which will hydrolyze to produce NH3 and H+.
The I- anion is the conjugate base of the strong acid HI. Therefore,
I- will not hydrolyze and the solution is acidic.

(b) The Na+ cation does not hydrolyze. The is the conjugate
base of the weak acid HNO2 and will hydrolyze to give HNO2 and
OH-. The solution will be basic.

(c) Both the and F- ions will hydrolyze. From Tables 15.3 and
15.4 we see that the Ka of (5.6 x 10-10) is greater than the Kb
for F- (1.4 x 10-11). Therefore, the solution will be acidic.

89 N.H.Seth
Practice 4.3.1

1. Predict whether a solution of ammonium nitrite ,

NH4NO2, will be acidic, basic, or neutral. Given Ka of
HNO2 = 4.6 X10-4 and Kb of NH3 =1.76 X10-5.

2. Predict whether aqueous solutions of the following are

acidic, basic or neutral. Write an equation for the
reaction of any ion with water.
a) KClO4
b) C6H5COONa
c) NaHSO4

N.H.Seth 90
 Relationship between Ka of an Acid
and Kb of Its Conjugate Base

• Kb values can be found from the given Ka values and

vice versa

when you add

equations, you
multiply the K’s

At 25 oC, Kw = 1 x 10 −14
N.H.Seth 91
 Example 4.3.2
Find the pH of 0.100 M NaCHO2(aq) solution

Kb for CHO2− = 5.6 x 10−11

Na+ is the cation of a CHO2− + H2O ⇔ HCHO2 + OH−
strong base – pH
neutral. The CHO2− [CHO2−] [HCHO2] [OH−]
is the anion of a weak
acid – pH basic initial 0.100 0 ≈0
write the reaction for
the anion with water
change
construct an ICE equilibrium
table for the reaction
enter the initial
concentrations –
assuming the [OH−]
from water is ≈ 0 N.H.Seth 92
 Example 4.3.2
represent the
change in the [CHO2−] [HCHO2] [OH−]
concentrations in
terms of x
initial 0.100 0 ≈0
sum the columns to change − +x +x
find the equilibrium equilibrium x
0.100 x x
concentrations in
−x
terms of x
Calculate the value
of Kb from the value
of Ka of the weak
acid from Table 15.5
substitute into the
equilibrium constant
expression
N.H.Seth 93
 Example 4.3.2
Kb for CHO2− = 5.6 x 10−11
substitute x into [CHO2−] [HCHO2] [OH−]
the equilibrium
initial 0.100 0 ≈0
concentration
definitions and cHAnge −x +x +x
solve equilibrium 0.100 2.4E-6 2.4E-6

x = 2.4 x 10−6

N.H.Seth 94
 Example 4.3.2
Kb for CHO2− = 5.6 x 10−11
use the [OH−] to
find the [H3O+] [CHO2−] [HCHO2] [OH−]
using Kw initial 0.100 0 ≈0
substitute [H3O+] change −x +x +x
into the formula
for pH and solve equilibrium 0.100 2.4E-6 2.4E-6

N.H.Seth 95
 Example 4.3.2
check by Kb for CHO2− = 5.6 x 10−11
substituting the [CHO2−] [HCHO2] [OH−]
equilibrium
concentrations initial 0.100 0 ≈0
back into the cHAnge −x +x +x
equilibrium
constant equilibrium 0.100 2.4E−6 2.4E−6
expression and
comparing the
calculated Kb to
the given Kb

though not exact,

the answer is
reasonably N.H.Seth
close 97
 Example of 4.3.3:
If a 0.15 M NaA solution has a pOH of 5.45, what is the Ka of HA?

Na+ is the cation of a A− + H2O ⇔ HA + OH−

strong base – pOH
neutral. Because
pOH is < 7, the [A−] [HA] [OH−]
solution is basic. A−
initial 0.15 0 ≈0
is basic.
write the reaction for
change
the anion with water equilibrium
construct an ICE
table for the reaction

enter the initial

concentrations –
assuming the [OH−]
from water is ≈ 0 N.H.Seth 98
 Example of 4.3.3:

use the pOH to [A−] [HA] [OH−]

find the [OH−]
initial 0.15 0 ≈0
use [OH−] to fill
cHAnge −3.6E−6 +3.6E−6 +3.6E−6
in other items
equilibrium 0.15 3.6E-6 3.6E-6

N.H.Seth 99
 Example of 4.3.3:

calculate the [A−] [HA] [OH−]

value of Kb of A−
initial 0.15 0 ≈0
change −3.6E−6 +3.6E−6 +3.6E−6
equilibrium 0.15 3.6E-6 3.6E-6

N.H.Seth 100
 Example of 4.3.3:

use Kb of A− to [A−] [HA] [OH−]

find Ka of HA
initial 0.15 0 ≈0
change −3.6E−6 +3.6E−6 +3.6E−6
equilibrium 0.15 3.6E-6 3.6E-6

N.H.Seth 101
Practice 4.3.2

• Calculate the pH of 0.5 M CH3COOK solution.

Determine whether the solution is acidic,
basic or neutral.

N.H.Seth 102
4.4 COMMON ION EFFECT

N.H.Seth 103
 Common Ion Effect
• A solution with two dissolved solutes that contain
SAME/COMMON ION (cation or anion)
• It will suppress the ionization of weak acid or weak base

The common ion effect is the shift in equilibrium caused by

the addition of a compound having an ion in common with the
dissolved substance.

N.H.Seth 104
 Common Ion Effect

The presence of a common ion suppresses the ionization of a

weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

N.H.Seth 105
 Common Ion Effect
Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq)
[H+][A-]
Ka =
HA (aq) + -
H (aq) + A (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch
equation
[HA]
-log [H+] = -log Ka - log
[A-]
[conjugate base]
pH = pKa + log
[A-] [acid]
-log [H+] = -log Ka + log
[HA]

[A-]
pH = pKa + log pKa = -log Ka
[HA] N.H.Seth 106
 Common Ion Effect
HA(aq) + H2O(l) ⇔ A−(aq) + H3O+(aq)

• Adding a salt, NaA containing the anion, A−(aq) which is the

conjugate base of the acid (the common ion), shifts the
position of equilibrium to the left, lowering the H3O+ ion
concentration
• This causes the pH to be higher than the pH of the acid
solution

N.H.Seth 107
 Buffers
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

An acid-base buffer is therefore a solution of a weak acid and its conjugate

base, or a weak base and its conjugate acid.

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.
Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
N.H.Seth 108
Example 4.4.1
Which of the following solutions can be classified as buffer systems?
(a) KH2PO4/H3PO4
(b) NaClO4/HClO4
(c) C5H5N/C5H5NHCl (C5H5N is pyridine; its Kb is given in Table 15.4)

Explain your answer.

Strategy
What constitutes a buffer system? Which of the preceding solutions
contains a weak acid and its salt (containing the weak conjugate
base)? Which of the preceding solutions contains a weak base and
its salt (containing the weak conjugate acid)? Why is the conjugate
base of a strong acid not able to neutralize an added acid?

109
Example 4.4.1
Solution The criteria for a buffer system is that we must have a weak
acid and its salt (containing the weak conjugate base) or a weak base
and its salt (containing the weak conjugate acid).

(a) H3PO4 is a weak acid, and its conjugate base, ,is a weak
base (see Table 15.5). Therefore, this is a buffer system.
(b) Because HClO4 is a strong acid, its conjugate base, , is an
extremely weak base. This means that the ion will not
combine with a H+ ion in solution to form HClO4. Thus, the system
cannot act as a buffer system.
(c) As Table 15.4 shows, C5H5N is a weak base and its conjugate
acid, C5H5N+H (the cation of the salt C5H5NHCl), is a weak acid.
Therefore, this is a buffer system.

110
Figure 4.4.1 The effect of adding acid or base to an unbuffered
and buffered solution.

A 100-mL sample of The addition of 1 mL of strong acid (left) or strong

dilute HCl is adjusted to base (right) changes the pH by several units.
pH 5.00.

A 100-mL sample of an The addition of 1 mL of strong acid (left) or

acetate buffer is strong base (right) changes the pH very little.
adjusted to pH 5.00. N.H.Seth 111
Buffers & the Common-ion Effect
A buffer works through the common-ion effect.

Example in acetic acid-acetate buffer system: Acetic acid

in water dissociates slightly to produce some acetate ion:
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
acetic acid acetate ion

If NaCH3COO is added, it provides a source of

CH3COO- ion, and the equilibrium shifts to the left.
CH3COO- is common to both solutions.

The addition of CH3COO- reduces the % dissociation of

the acid.
N.H.Seth 112
 How a Buffer Works
The buffer components (HA and A-) are able to consume
small amounts of added OH- or H3O+ by a shift in
equilibrium position.

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Added OH- reacts with Added H3O+ reacts with

CH3COOH, causing a shift to CH3COO-, causing a
the right. shift to the left.

The shift in equilibrium position absorbs the change in

[H3O+] or [OH-], and the pH changes only slightly.

N.H.Seth 113
 Figure 4.4.2 How a buffer works.
Buffer has more HA after Buffer has equal Buffer has more A- after
addition of H3O+. concentrations of A- and HA. addition of OH-.

H3O+ OH-

H2O + CH3COOH ← H3O+ + CH3COO- CH3COOH + OH- → CH3COO- + H2O

N.H.Seth 114
 Buffer Capacity
The buffer capacity is a measure of the “strength” of the
buffer, its ability to maintain the pH following addition of acid,
H+ or base, OH- ion.
The greater the concentrations of the buffer components, the
greater its capacity to resist pH changes.

The closer the component concentrations are to each other,

the greater the buffer capacity.
A buffer whose pH is equal to or near the pKa of its acid component has the
highest buffer capacity.

The pH of a buffer is distinct from its buffer capacity.

QUALITATIVELY:
⮚ Buffer maintains its pH if
[number mole of added base] ≤ [number mole of HA present in buffer]
[number mole of added acid] ≤ [number
N.H.Seth
mole of A- present in buffer] 115
 Buffer Range
The buffer range is the pH range over which the buffer is
effective.
Buffer range is related to the ratio of buffer component
concentrations.
[HA]
The closer - is to 1, the more effective the buffer.
[A ]

If one component is more than 10 times the other, buffering

action is poor. Since log10 = 1, buffers have a usable
range within ± 1 pH unit of the pKa of the acid
component.

N.H.Seth 116
 Types of Buffer
1. Acidic buffer (keep the pH below 7)
❖ It consists of a weak acid and a salt of the weak acid
(the conjugate base of the weak acid).

1. Basic buffer (keep the pH above 7)

❖ It consists of a weak base and a salt of the weak base
(the conjugate acid of the weak base).

N.H.Seth 117
 Preparing a Buffer
• Choose the conjugate acid-base pair.
– The pKa of the weak acid component should be close to the
desired pH.
• Calculate the ratio of buffer component concentrations.
[base]
pH = pKa + log
[acid]

• Determine the buffer concentration, and calculate the

required volume of stock solutions and/or masses of
components.
• Mix the solution and correct the pH.

N.H.Seth 118
Henderson-Hasselbalch Equation
and pH of Buffers
HA(aq) + H2O(l) A-(aq) + H3O+(aq)

[H3O+][A-] [HA]
Ka = [H3O+] = Ka x
[HA] [A-]

[HA]
-log[H3 O +] = -logKa – log
[A-]

[conj. base]
pH = pKa + log
[acid]

N.H.Seth 119
Henderson-Hasselbalch Equation
and pH of Buffers

❖ pH of acidic buffer:

pH = pKa + log [conjugate base]

[acid]

❖ pH of basic buffer:

pOH = pKb + log [conjugate acid]

[base]
N.H.Seth 120
 Example 4.4.2 :
What is the pH of a buffer that is 0.100 M HC2H3O2
and 0.100 M NaC2H3O2?

write the reaction Ka for HC2H3O2 = 1.8 x 10−5

for the acid with
water HC2H3O2 + H2O ⇔ C2H3O2− + H3O+
construct an ICE [HC2H3O2] [C2H3O2−] [H+]
table for the initial 0.100 0.100 ≈0
reaction
enter the initial
change
concentrations – equilibrium
assuming the
[H3O+] from
water is ≈ 0
N.H.Seth 121
 Example 4.4.2 :

represent the HC2H3O2 + H2O ⇔ C2H3O2− + H3O+

change in the
concentrations in [HC2H3O2] [C2H3O2−] [H+]
terms of x initial 0.100 0.100 0
sum the columns change − +x +x
to find the
x −x 0.100 + x
equilibrium 0.100 x
equilibrium
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
N.H.Seth 122
 Example 4.4.2 :

Ka for HC2H3O2 = 1.8 x 10−5

determine the [HA] [A−] [H3O+]

value of Ka
initial 0.100 0.100 ≈0
because Ka is very
small, approximate change −x +x +x
the [HA]eq = [HA]init equilibrium 0.100
0.100−x 0.100
0.100+x x
and [A−]eq = [A−]init ,
then solve for x

N.H.Seth 123
 Example 4.4.2 :

Ka for HC2H3O2 = 1.8 x 10−5

check if the [HC2H3O2] [C2H3O2−] [H+]

approximation
initial 0.100 0.100 ≈0
is valid by
seeing if x < cHAnge −x +x +x
5% of equilibrium 0.100 0.100 x
[HC2H3O2]init
x = 1.8 x 10−5

N.H.Seth 124
 Example 4.4.2 :

substitute x [HC2H3O2] [C2H3O2−] [H+]

into the
initial 0.100 0.100 ≈0
equilibrium
concentration change −x +x +x
definitions equilibrium 0.100
0.100 0.100
0.100 x
+ x 1.8E-5
and solve −x
x = 1.8 x 10 −5

N.H.Seth 125
 Example 4.4.2 :

[HC2H3O2] [C2H3O2−] [H+]

substitute [H3O+]
into the formula initial 0.100 0.100 ≈0
for pH and solve change −x +x +x
equilibrium 0.100 0.100 1.8E−5

N.H.Seth 126
Example 4.4.2 :

ALTERNATIVE METHOD:
Ka for HC2H3O2 = 1.8 x 10−5
pKa = - log 1.8 x 10−5
= 4.74
[CH3O2-]
pH = pKa + log
[HC2H3O2]

[0.10]
pH = 4.74 + log = 4.74
[0.10]

N.H.Seth 127
Example 4.4.3:

Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer

system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
(pKa= 9.25)

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3]
pH = pKa + log
[NH4+]

[0.30]
pH = 9.25 + log = 9.17
[0.36]
N.H.Seth 128
Example 4.4.3:
NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)

start (moles) 0.02 0.00 0.02

9 1 4
end (moles) 0.02 0. 0.02
8 0 5
final volume = 80.0 mL + 20.0 mL = 100 mL
0.028 mol 0.02
[NH4+] = = 0.28 M [NH3] = 5 = 0.25 M
0.10 L 0.1
0

[0.25]
pH = 9.25 + log = 9.20
[0.28]

N.H.Seth 129
Functions of Buffer Solutions
• Calibration of pH meter
• Controlling dye process
• Manufacturing pharmaceuticals
• Human body uses buffers to maintain blood pH of 7.35-
7.45 and maintain certain pH for optimum pH conditions
for certain enzymes

N.H.Seth 130
 Practice 4.4.1
1. Which one of the following combinations cannot function as a buffer
solution?
A) HCN and KCN D) HF and NaF
B) NH3 and (NH4)2SO4 E) HNO2 and NaNO2
C) HNO3 and NaNO3

2. Assuming equal concentrations of conjugate base and acid, which

one of the following mixtures is suitable for making a buffer solution
with an optimum pH of 9.2–9.3?
A) CH3COONa / CH3COOH (Ka = 1.8 × 10–5)
B) NH3 / NH4Cl (Ka = 5.6 × 10–10)
C) NaOCl / HOCl (Ka = 3.2 × 10–8)
D) NaNO2 / HNO2 (Ka = 4.5 × 10–4)

N.H.Seth 131
Practice 4.4.1

3. Consider a buffer solution prepared from HOCl and NaOCl. Write

the net ionic equation for the reaction that occurs when NaOH is
added to this buffer.

4. Calculate the pH of a buffer solution that contains 0.25 M benzoic

acid (C6H5CO2H) and 0.15M sodium benzoate (C6H5COONa). [Ka =
6.5 × 10–5 for benzoic acid] Ans: 3.97

5. Calculate the pH of a buffer solution prepared by dissolving 0.20

mole of cyanic acid (HCNO) and 0.80 mole of sodium cyanate
(NaCNO) in enough water to make 1.0 liter of solution. Ans: 4.3
[Ka(HCNO) = 2.0 × 10–4]

N.H.Seth 132
4.5 ACID-BASE TITRATION
CURVE & INDICATORS

Volumetric Analysis
(Titration)

N.H.Seth 133
 Acid-Base Titrations
In an acid-base titration, the concentration of an acid (or a
base) is determined by neutralizing the acid (or base) with
a solution of base (or acid) of known concentration.

The equivalence point of the reaction occurs when the

number of moles of OH- added equals the number of
moles of H3O+ originally present, or vice versa.
The equivalence point with one pH value only.

The end point occurs when the indicator changes color.

- The indicator should be selected so that its color change occurs at a
pH close to that of the equivalence point.
- In the range of pH at steep portion of the titration curve

N.H.Seth 134
Figure 4.5.1 Curve for a strong acid–strong base titration.

The pH increases gradually

when excess base has been
added.

The pH rises very rapidly

at the equivalence point,
which occurs at pH = 7.00.

The initial pH is low.

N.H.Seth 135
❖ For a general acid-base reaction:

Ma and Va = molarity and volume of acid

Mb and Vb = molarity and volume of base
a and b = stoichiometric reaction coefficients
N.H.Seth 136
Practices 4.5.1

Exactly 21.0 mL of a 0.1 M NaOH solution was

required to completely titrate 20.0 mL of H2SO4
solution. What is the concentration of the acid
in molar and gL-1? (MM of H2SO4: 98g/mol)

Answer = 0.053 M and 5.194 gL-1

N.H.Seth 137
 Titration Curve
❖ A graph of pH versus volume of titrant added (the
solution in the burette) is called titration curve

Equivalence
Titration pH change
point

Strong acid-strong
pH 7 3.5 - 9.5
base
Strong acid-weak base pH < 7 3.0 – 7.0
Weak acid-strong base pH > 7 6.5 – 10.5
Weak acid-weak base Not obvious Not obvious
N.H.Seth 138
 Titration Curve

Base in the burette Acid in the burette

Acid in the beaker Base in the beaker

N.H.Seth 139
Strong Acid-Strong Base Titrations
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)
OH- (aq) + H+ (aq) H2O (l)

N.H.Seth 140
 Calculating the pH during a
strong acid–strong base titration
Initial pH
If acid in the beaker :
[H3O+] = [HA]init
pH = -log[H3O+]
If base in the beaker:
[OH-] = [BOH]init
pOH = -log[OH- ] pH = 14 - pOH

pH at the equivalence point

pH = 7.00 for a strong acid-strong base titration.

N.H.Seth 141
 Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

Equivalence
point

Buffer region

N.H.Seth 142
 Calculating the pH during a
weak acid–strong base titration

Initial pH
[H3O+][A-]
Ka = [H3O+] =
[HA]
pH = -log[H3O+]

pH before equivalence point pH at the equivalence point

(in the buffer region) A-(aq) + H2O(l) HA(aq) + OH-(aq)
[HA [OH- ] =
[H3O+] = Ka x or
]
mol HAinit Kw
[A-] where [A-] = and Kb =
[bas Vacid + Vbase Ka
pH = pKa + log
e]
Kw
[acid] [H3O+] ≈ and pH = -log[H3O+]

N.H.Seth 143
 Example 4.5.1
25.0 mL of 0.100 M NaOH reacting with 25.0 mL of 0.100 M CH3COOH
in a titration. Calculate the pH of solution at the equivalence point.

The number of moles of NaOH in 25.0 mL of the solution is

The changes in number of moles are summarized next:

CH3COOH (aq) + NaOH (aq) → CH3COONa(aq) + H2O(l)

Initial (mol): 2.50 x 10-3 2.50 x 10-3 0
Change (mol): -2.50 x 10-3 -2.50 x 10-3 +2.50 x 10-3
Final (mol): 0 0 2.50 x 10-3

144 N.H.Seth
 Example 4.5.1

At the equivalence point, the concentrations of both the acid and the base
are zero. The total volume is (25.0 + 25.0) mL or 50.0 mL, so the
concentration of the salt is

The next step is to calculate the pH of the solution that results from the
hydrolysis of the CH3COO- ions.

145
 Example 4.5.1

Following the procedure described in Example 15.13 and looking up the

base ionization constant (Kb) for CH3COO- in Table 15.3, we write

146
 Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4+ (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

Buffer region

Equivalence
point

N.H.Seth 147
Example 4.5.2
Calculate the pH at the equivalence point when 25.0 mL of 0.100 M NH3 is
titrated by a 0.100 M HCl solution.

Strategy
The reaction between NH3 and HCl is

NH3(aq) + HCl(aq) NH4Cl(aq)

We see that 1 mol NH3 Ξ 1 mol HCl. At the equivalence point, the major
species in solution are the salt NH4Cl (dissociated into and Cl- ions) and
H2O. First, we determine the concentration of NH4Cl formed. Then we
calculate the pH as a result of the ion hydrolysis. The Cl- ion, being the
conjugate base of a strong acid HCl, does not react with water. As usual, we
ignore the ionization of water.

148 N.H.Seth
Example 4.5.2
Solution The number of moles of NH3 in 25.0 mL of 0.100 M
solution is

At the equivalence point the number of moles of HCl added equals the
number of moles of NH3. The changes in number of moles are summarized
below:

NH3(aq) + HCl(aq) → NH4Cl(aq)

Initial (mol): 2.50 x 10-3 2.50 x 10-3 0
Change (mol): -2.50 x 10-3 -2.50 x 10-3 + 2.50 x 10-3
Final (mol): 0 0 2.50 x 10-3

149 N.H.Seth
Example 4.5.2

At the equivalence point, the concentrations of both the acid and the base are zero.
The total volume is (25.0 + 25.0) mL, or 50.0 mL, so the concentration of the salt is

The pH of the solution at the equivalence point is determined by the hydrolysis of

ions.

150 N.H.Seth
Example 4.5.2

Step 1: We represent the hydrolysis of the cation , and let x be the

equilibrium concentration of NH3 and H+ ions in mol/L:

(aq) NH3(aq) + H+(aq)

Initial (M): 0.0500 0.000 0.000
Change (M): -x +x +x
Equilibrium (M): (0.0500-x) x x

151 N.H.Seth
Example 4.5.2
Step 2: From Table 15.4 we obtain the Ka for :

Applying the approximation 0.0500 - x ≈ 0.0500, we get

Thus, the pH is given by

pH = -log (5.3 x 10-6)

= 5.28

152 N.H.Seth
Example 4.5.3

Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M

100 mL NaOH solution. What is the pH at the equivalence
point ?
HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)

start (moles) 0.0 0.0 0.

1 1 0
end (moles) 0. 0. 0.0
0 0 1

Final volume = 200 mL

0.0
[NO2-] = = 0.05 M
0.20
1
0
Na+ is not included in the equation as it is the conjugate acid of strong
base (completely dissociate, notN.H.Seth
involve in futher dissociation with water)153
Example 4.5.3
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

I 0.0 0.0 0.0

5 0 0
C -x +x +x
E 0.05 - x x x

[OH-][HNO2] x2
Kb = = = 2.2 x 10-11
-
[NO2 ] 0.05-
x
0.05 – x ≈ 0.05
pOH = 5.98
-
x ≈ 1.05 x 10-6 = [OH ]
pH = 14 – pOH = 8.02

N.H.Seth 154
Practice 4.5
A solution of 50 cm3 of an acid HA is titrated with 0.1 M of a strong base
M(OH)2. Phenolphthalein is added as an indicator. Exactly 16.5 cm3 of
M(OH)2 has been added when the colour of the solution changes from
colourless to pink. (pKa for HA = 4.87)

a) Explain the terms “equivalence point” and ”end point”.

b) Calculate the molarity of the acid HA. (0.066M)
c) Calculate the pH of the original solution of HA. (3.03)
d) What is the pH of the solution when the original acid solution is half-
neutralised? (buffer condition) (4.87)
e) Calculate the pH of the solution at the equivalence point.
(8.78)
f) Sketch a titration curve of pH versus volume of M(OH)2 added.

N.H.Seth 155
4.5 e) Calculate the pH of the solution at the equivalence point.

Titration:
Mol HA = 0.066M x 0.05L = 3.3x10-3 mol
Mol M(OH) 2 = 0.1M x 0.0165L = 1.65x10-3 mol

HA (aq) + M(OH)2- (aq) MA2 (aq) + H2O (l)

Mol start 3.3x10-3 1.65x10-3
Mol end 1.65x10-3
** mol of salt = mol of strong base (completely dissociate)

Salt dissociation:
MA2 (aq) M2+ (aq) + 2A- (aq)

1 mol of MA2 2 mol A-

So, 1.65x10-3mol 3.3x10-3 mol A-

[A-] = 3.3x10-3 mol / 0.0665L = 0.05M

N.H.Seth 156
4.5 e) Calculate the pH of the solution at the equivalence point.

Hydrolysis:
A- (aq) + H2O (l) HA(aq) + OH- (aq)
I 0.05 0 0
C -x +x +x
E 0.05 – x +x +x

Kw = Ka Kb pKa = 4.87
Kb = Kw / Ka Ka = 1.35 x10-5
= 1.0 x10-14 /1.35 x10-5
= 7.41 x10-10

[OH-][HA] x2
Kb = = = 7.41 x10-10
[A-] 0.05-
x
0.05 – x ≈ 0.05
pOH = 5.22
-
x ≈ 6.08 x 10-6 = [OH ]
pH = 14 – pOH = 8.78
N.H.Seth 157
4.5 e) Calculate the pH of the solution at the equivalence point.

ALTERNATIVE METHOD:

[OH-] = √ c . Kb
= √ (0.05)(7.41 x10-10)
= 6.08 x 10-6

pOH = 5.22

pH = 14 – pOH = 8.78

N.H.Seth 158
 Acid-base Indicators
An acid-base indicator is a weak organic acid (HIn) or a dye
whose color differs from that of its conjugate base (In-).

• Many dyes change color depending on the pH of the solution

• These dyes establishing an equilibrium with the H2O and H3O+ in
the solution: HInd(aq) + H2O(l) ⇔ Ind−(aq) + H3O+(aq)

The ratio [HIn]/[In-] is governed by the [H3O+] of the solution. Indicators

can therefore be used to monitor the pH change during an acid-base
reaction.
• The color of the solution depends on the relative concentrations
of Ind−:HInd
– when Ind−:HInd ≈ 1, the color will be mix of the colors of Ind− and HInd
– when Ind−:HInd > 10, the color will be mix of the colors of Ind−
– when Ind−:HInd < 0.1, the color will be mix of the colors of Hind
N.H.Seth 159
 Acid-base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
≥ 10 Color of acid (HIn) predominates
[In-]

[HIn]
≤ 10 Color of conjugate base (In-) predominates
[In-]

N.H.Seth 160
 Monitoring a Titration with an
Indicator
• For most titrations, the titration curve shows a very large
change in pH for very small additions of titrant near the
equivalence point
• An indicator can therefore be used to determine the
endpoint of the titration if:
– pKa of indicator ≈ pH at equivalence point
– it changes color within the same range as the rapid
change in pH

N.H.Seth 161
Colors and approximate pH range of
some common acid-base indicators.
pH

N.H.Seth 162
Acid-Base Indicators

N.H.Seth 163
Solutions of Red Cabbage Extract

pH

N.H.Seth 164
The titration curve of a strong acid with a strong base.

N.H.Seth 165
Example 4.5.4
Which indicator or indicators listed in Table 16.1 would you use for the acid-base
titrations shown in

Strategy
The choice of an indicator for a particular titration is based on the fact that its pH
range for color change must overlap the steep portion of the titration curve.
Otherwise we cannot use the color change to locate the equivalence point.

(a) Figure 16.4?

(a) Near the
equivalence point, the
pH of the solution
changes abruptly from 4
to 10. Therefore, all the
indicators except thymol
blue, bromophenol blue,
and methyl orange are
suitable for use in the
titration.

166 N.H.Seth
Example 4.5.4

(b) Figure 16.5?

(b) Here the steep portion covers the pH range between 7 and 10;
therefore, the suitable indicators are cresol red and phenolphthalein.

167 N.H.Seth
Example 4.5.4

(c) Figure 16.6?

Here the steep portion of the pH curve covers the pH range between 3
and 7; therefore, the suitable indicators are bromophenol blue, methyl
orange, methyl red, and chlorophenol blue.

168 N.H.Seth
Phenolphthalein

N.H.Seth 169
Methyl Red

N.H.Seth 170
 SUMMARY
✔ Define acid-base according to Arrhenius, Bronsted-
Lowry and Lewis theories
✔ Identify conjugate pairs for acid-base (Bronsted-Lowry)
✔ Define and identify strong and weak acid base
✔ Calculate pH, pOH, Kw, Ka, Kb, pKa, pKb and determine
relationship among them
✔ Explain and draw titration curve
✔ Define buffer solution and perform
Henderson_hasselbalch Equation and pH of buffer
N.H.Seth 171
 pH CALCULATION
STRONG
WEAK ACID
ACID /
/ WEAK TITRATION BUFFER
STRONG
BASE
BASE
SA+SB; HENDERSON-
MaVa/MbVb HASSELBALCH
pH = - log [H+] Ka, [H+], pH =a/b EQUATION

SA+WB=Acidi pH = pKa + log

[A-]
c
Ka, [H+], pH [HA]

Kb, [OH-], pOH,

pOH = - log [OH-] SB+WA=Basic pOH = pKb + log
pH [BOH]
Kb, [OH-],
pOH, pH [BH+]

N.H.Seth 172