CHAPTER 7:

IONIC
EQUILIBRIA
7.1 ACIDS AND BASES
Students should be able to:
a) define acids and bases according to the Arrhenius and
Bronsted-Lowry theories
b) identify conjugate acid and conjugate base according to
Bronsted-Lowry theory.
c) relate pH and pOH to the ionic product of water, Kw at 25°C.
7.1 ACIDS AND BASES
Students should be able to:
d) define strong acid and base, weak acid and base, pH, pOH and
p Kw.
e) calculate the pH values of a strong acid and base.
f) relate the strength of weak acid and weak base to the
respective dissociation constants, Ka and Kb.
7.1 ACIDS AND BASES
Students should be able to:
g) perform calculations involving :
i) pH
ii) dissociation constant
iii) initial concentration and equilibrium concentration
iv) degree of dissociation
(perform calculations only on weak monoprotic acids
and weak bases)
7.1 ACIDS AND BASES
Students should be able to:
h) explain qualitatively salt hydrolysis using hydrolysis equations
and classify the salts formed from the reaction between:
i) strong acid and strong base
ii) strong acid and weak base
iii) weak acid and strong base
i) define buffer solution
j) describe how a buffer solution controls its pH.
7.1 ACIDS AND BASES
Students should be able to:
k) write the Henderson-Hasselbalch equation for a given buffer
solution.
l) calculate the pH of buffer solutions using the Henderson-
Hasselbalch equation before and after the addition of strong acid
or base.
7.1 ACIDS AND BASES
Theory of Acids and Bases

Three important theories

1. Arrhenius theory
2. Bronsted-Lowry’s theory
3. Lewis theory

7
Theory of Acids and Bases

1. Arrhenius Theory

Acid:
any substance that produces hydrogen ion (H+) or
hydronium ion (H3O+) when dissociating in water.

Example:

HCl (aq) H+ (aq) + Cl− (aq)

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

8
Base:
any substance that produces hydroxide ions (OH-)
when dissociating in water.

Example:

NaOH (aq) Na+ (aq) + OH− (aq)

9
 2. Bronsted-Lowry Theory
Acid:
any substance that can donate a proton, (H+) to other
substance

Example:

HNO3 (aq) + H2O (l) NO3− (aq) + H3O+ (aq)

acid

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

acid
10
Base:
any substance that can accept a proton from other substance

Example:
NH3 (aq) + H2O (l) NH4+ (aq) + OH− (aq)
base

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

base

H2O is able to act as an acid or a base : AMPHOTERIC

11
Conjugate Acid-base Pairs

⚫Conjugate base
◦ A species that remains when one proton has been
removed from the Bronsted acid.

⚫Conjugate acid
◦ A species that remains when one proton has been
added to the Bronsted base.
12
Example

HCO3− (aq) + H2O (l) CO32− (aq) + H3O+(aq)

acid base conjugate conjugate
base acid

⚫The stronger the acid, the weaker is its conjugate base and
the stronger the base, the weaker is its conjugate acid.

13
 CONCEPTS OF CONJUGATE ACIDS AND BASES

Acid: proton donor Base: proton acceptor

Conjugate base: Species that Conjugate acid: Species that formed

formed when an acid donates when a base accepts proton (H+)
proton (H+)

HCO3 (aq) + H2O (l) ⇌ CO32 (aq) + H3O+(aq)

Acid Base conjugate conjugate
base acid
*Arrow and label are compulsory
The stronger the acid/ base, the weaker its conjugate acid/conjugate base pair
Exercise
1. In the following reactions, identify the acid-base conjugate
pairs.

a. ClO− (aq) + H2O (l) HOCl (aq) + OH− (aq)

b. CH3NH2 (aq) + H2PO4- (aq) CH3NH3+(aq) + HPO42− (aq)

c. HBr(aq) + NH3(aq) NH4+(aq) + Br− (aq)

d. PO43−(aq) + H2O(l) HPO42−(aq) + OH−(aq)

e. CH3COOH(aq) + H2O(l) CH3COO−(aq) + H3O+(aq) 15

2. Write the conjugate base formula for the following acids.
a) HS− d) H3PO4
b) HCN e) H3O+
c) N2H5+ f) CH3NH3+

3. Write the conjugate acid formula for the following bases.

a) HS- d) NH3
b) C6H5COO− e) H2O
c) OH− f) H2PO4−

16
3. Lewis Theory

Acid:
a substance that can accept a pair of electrons to form a
covalent bond.

The species that can be Lewis acid are

● Cations such as H+, Fe2+, Al3+

●molecules with incomplete octet central atom such as BF3,
BeCl2
● Molecules with central atom that can expand octet such as
PCl3 17
Base:
a substance that can donate a pair of electrons to form a
covalent bond.

The species that can be Lewis base are

● anions such as OH-, CN-, Cl-
● molecules with lone pairs electrons at
the central atom such as H2O, NH3, ROH
● molecules with nonpolar multiple bond such as alkenes

18
 Example
1) H3N: + BF3 H3N→ BF3
Lewis Lewis
base acid

2) H+ + OH- H2O
Lewis Lewis
acid base

3) 2Cl-(aq) + SnCl4 (aq) SnCl62-(aq)

Lewis Lewis
base acid

19
Exercise
Classify each of the following species as Lewis acid or Lewis
base.

i. NH3
ii. AlCl3
iii. BCl3
iv. Ag+
v. I-

20
 DEFINITION OF ACIDS AND BASES

Theory Definition
Acid Base

Arrhenius Produce H+ or H3O+ ion Produce OH- ion

Bronsted-Lowry Proton (H+) donor Proton (H+) acceptor

Lewis Electron pair acceptor Electron pair donor

 DEFINITION OF STRONG ACIDS
AND BASES AND WEAK ACIDS AND
Acid
BASES Base
Strong Ionize completely in an aqueous solution to Ionize completely in an aqueous solution to
produce high concentration of H+ or H3O+ ion. produce high concentration of OH- ion.

HCl (aq) →H+ (aq) + Cl− (aq) NaOH (aq) → Na+ (aq) + OH− (aq)

Eg: HCl, HBr, HI, HNO3, H2SO4, HClO4 Eg: NaOH, LiOH, Ca(OH)2, Mg(OH)2
(Hydroxides of cations from Group 1 and
Group 2 elements)

Weak Ionize partially in an aqueous solution to Ionize partially in an aqueous solution to

produce low concentration of H+ or H3O+ ion. produce low concentration of OH- ion.

HCOOH(aq) + H2O(l) NH3(aq) + H2O (l) NH4+ (aq) + OH- (aq)

H3O+ (aq) + HCOO- (aq)

Eg: HF, HCN, HNO2, carboxylic acids like Eg: NH3, CH3NH2, C5H5N (contains N)
HCOOH, CH3COOH
⚫The strong acids are ...

◦ The hydrohalic acids HCl, HBr and HI

◦ Oxoacids in which the number of O atoms exceeds

the number of ionizable protons by two or more
e.g: HNO3 and HClO4

23
⚫The strong bases...

◦ M2O or MOH, where M is group 1 element :

Li, Na, K, Rb, Cs

◦ RO or R(OH)2, where R is Ca, Sr, Ba

24
⚫The weak acids are ....

◦ The hydrohalic acids HF

◦ Acids in which H is not bonded to O or to halogen

e.g: HCN and H2S

◦ Oxoacids in which the number of O atoms equals or

exceeds by one the number of ionizable protons
e.g: HNO2 and HClO

◦ Organic acids (general formula RCOOH)

e.g: CH3COOH

25
⚫ The weak bases are ...

◦ Ammonia (NH3)

◦ Amines with general formula RNH2, R2NH, R3N

e.g. : CH3CH2NH2; (CH3)2NH; (CH3)3N

26
The pH Scale

• The pH scale is used to express acidity.

• The pH of a solution is defined as the negative

logarithm (log) of the hydroxonium ion (hydrogen
ion) concentration.

pH = − log [H3O+]

• In similar way, pOH is the negative logarithm of the

hydroxide ion concentration.

pOH = − log [OH−]

27
At 25 oC,

◦ Acidic solution : pH < 7.0 ; pOH > 7.0

◦ Basic solution : pH > 7.0 ; pOH < 7.0

◦ Neutral solution : pH = 7.0 ; pOH = 7.0

pH scale

0 7 14
acidic neutral basic
[H+]>[OH-] [H+]=[OH-] [H+]<[OH-]
◦ 28
The Water Ionization Constant, Kw

• When water molecules ionized, transferring a proton from one

water molecule to another producing a hydroxonium and
hydroxide ion.

2H2O (l) H3O+ (aq) + OH− (aq)

• The equilibrium constant expression can be written as follows:

∴ Kw = [H3O+] [OH-]

• Kw is the ionization constant for water at 25°C

29
For pure water, at 25°C,

[H3O+] = [OH−] = 1 x 10-7 M

Kw = [H3O+] [OH−]
= (1 x 10-7) (1 x 10-7)

∴ Kw = 1 x 10-14 M2

Note:
Increase the temperature will increase the Kw value because the
dissociation of water is an endothermic process

30
In pure water,

Kw = [H3O+] [OH−] = 1 x 10-14 M2

- log Kw = - log ([H3O+] [OH−])

- log Kw = - log [H3O+] + (- log [OH−])

pKw = pH + pOH

∴ 14 = pH + pOH

31
Formula/ Relationship:

1) pH = -log [H+]

2) pOH = -log [OH-]

3) pH + pOH = pK
w
= 14

4) K
w
= [H+] [OH-] = 1 x 10-14 M2

5) pK
w
= -log K
w
= 14

6) pK = -log K
a a

7) pK = -log K
b b

8) K xK =K
a b w

9) pK + pK = pK = 14
a b w

pH scale

32

0 7 14
 Calculating pH value of Strong Acid

STEP 1 STEP 2 STEP 3

Write the dissociation [H+]=[Strong acid] Calculate the pH
equation of strong acid. value.
Phases are compulsory.
pH = -log [H+]
HA(aq)→ H+(aq)+A-(aq)
Step 1: Step 4:
Write the dissociation equation Calculate the pH
of strong base. value.
Phases are compulsory. pH = 14 - pOH

XOH(aq)→ X+(aq)+OH-(aq)
Calculating
pH value of
Strong Base

Step 3:
Step 2:
Calculate the pOH
[OH-]=[Strong base]
value.
pOH = -log [OH-]
Example 1: Calculate the pH of 0.15 mol dm-3 of HCl solution.
HCl(aq) H+(aq) + Cl-(aq)

0.15M 0.15M 0.15M

pH = - log [H+]
= - log (0.15 M)
= 0.82
Example 2: Calculate the pH of 0.1 mol dm-3 of Ca(OH)2 solution.

Ca(OH)2(aq) Ca2+(aq) + 2OH-(aq)

0.1M 0.1M 0.2M

pOH = - log [OH-]

= - log (0.2 M)
= 0.7

pH = 14 –pOH
= 14 -0.7
= 13.3
 Acids and Bases Dissociation Constant
Acid dissociation constant K a Base dissociation constant Kb

Indicates the strength of a weak acid Indicates the strength of a weak base

HF(aq) + H2O (l) H3O+(aq)+F-(aq) NH3(aq) + H2O (l) NH4+(aq)+OH-(aq)

Ka = [F-] [H3O+] Ka x Kb = Kw Kb = [OH-] [NH4+]

[HF] [NH3]

pKa = -log Ka pKa + pKb = pKw pKb = -log Kb

Strength Ka pKa [H3O+] pH Strength Kb pKb [OH-] pOH pH

Stronger Large Small High Small Stronger Large Small High Small Large
acid base
Weaker Small Large Low Large Weaker Small Large Low Large Small
acid base

<7 >7
Example 1 :
Based on the value of pKb, arrange the following compounds in order of increasing
strength of base.

Compound pKb
NH2OH 7.9
N2H4 5.8
NH3 4.7
C6H5NH2 9.4

Answer : C6H5NH2 < NH2OH < N2H4 < NH3

Exercise 1 :
Complete the following table.
Base Conjugate Kb pKa
acid
N2H4 1.3 x 10-6
NH2OH 1.1 x 10-8
NH3 1.8 x 10-5
C5H5N 1.7 x 10-9
a) Based on the value of Kb, arrange the bases in order of increasing strength.
b) Based on the value of pKa, arrange the conjugate acids in order of increasing
strength.
DEGREE OF DISSOCIATION, Α
α = [H+] or [OH-] ion dissociated
initial [acid] or [base]

α = [H+] or [OH-] ion dissociated x 100

initial [weak acid] or [weak base]

For strong acid and strong base, complete dissociation

occurs if α = 1 or 100%
 Guidelines of Calculating
STEP 4 pH value of Weak Acid STEP 5
(Monoprotic) or Weak
For weak acid and weak base with From x, find pH.
Base For weak acid, x = [H+]
small Ka & Kb (= 10 or <10 ),
-5 -5
pH = -log [H+]
approximation method is applied.
For weak base, x = [OH-]
pOH = -log [OH-]
STEP 3 pH = 14- pOH
Construct ICE table to determine the [H+] or [OH-] that
represented by x value.
Use Ka/Kb value or use α to find x.

STEP 2
STEP 1 Write
List down the equation(⇌)
information given. Phases are
compulsory.
Example 1 :
The base-dissociation constant for ammonia, NH3(aq) is 1.8 x 10-5 M. Calculate the
concentration of OH- ion, pH and percentage dissociation at equilibrium if the initial
concentration of NH3 is 0.15 M.

Solution : NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

 At equilibrium, Kb = [NH4+] [OH-]
[NH3]
= (x) (x)
0.15-x
= 1.8 x 10-5 M

Assume x is too small, 0.15-x ≈ 0.15

X2
0.15
= 1.8 x 10 -5
M
x2 = (1.8 x 10-5 M) (0.15 M)
x = 1.64 x 10-3 M = [OH-]
Therefore,
pOH = -log [OH-]
= -log (1.64 x 10-3)
= 2.79

pH = 14 - pOH
pH = 14 – 2.79
= 11. 21
 % 1.64
α = x 10-3 x 100
0.15
= 1.09 %

≈ 1.1 %

Degree of dissociation, α = 0.011

Example 2 :
The percentage of dissociation for 0.10 M pyridine, C 5H5N is 0.012%.
Calculate its base dissociation constant, Kb and its pH.

Solution : C5H5N(aq) + H2O(l) C5H5NH+(aq) + OH-(aq)

[ ]/M C5H5N C5H5NH+ OH-

[ ]i 0.10 0 0
[ ]c -x +x +x
[ ]e 0.10-x x x
%α = x x 100
0.10
0.012 = x x 100
0.10
x = 1.2 x 10-5

Kb = [C5H5NH+] [OH-]
[C5H5N] x= [OH-] = 1.2 x 10-5 M
= (x) (x)
pOH = -log [OH-]
0.10 - x = -log 1.2 x 10-5
= (1.2 x 10-5) (1.2 x 10-5) = 4.82
0.10- (1.2 x 10-5)
pH = 14 - 4.82
= 1.44 x 10-9 = 9.18
 Try this…
Acid dissociation constant, K for hydrofluoric acid HF at 25 C is 6.8104 M. For a solution of 0.20 M HF, calculate:
1. a
a. the concentration of hydronium ion at equilibrium

b. degree of dissociation

The percentage of dissociation for 0.25 M ammonia, C H N is 0.017%. Calculate its base dissociation constant, K
2. 5 5 b
and its pH value.

48
 Exercises
1. The Ka for benzoic acid, (C6H5COOH) is 6.5x10-5. Calculate the pH
of a 0.25 M benzoic acid solution.
(2.39)

2. The pH of an acid solution is 6.20. Calculate the Ka for the acid. The
acid concentration is 0.01M.
(3.98 x 10-11)

3. Calculate the pH for 0.5M C5H5N. Kb = 1.7x10-9

(9.47)

49
4. Calculate pH for the following solution.

Answer
a. 0.55 M CH3COOH (Ka = 1.8x10-5) 2.5
b. 0.23 M NH3 (Kb = 1.8x10-5) 11.31
c. 0.15 M HCl 0.82
d. 0.20 M KOH 13.3
e. 0.45 M HCN (Ka = 4.9 x 10-10) 4.8

50
 SALT HYDROLYSIS
⚫ Salt hydrolysis is a chemical reaction between anion or cation of a salt
with water molecules.
⚫ Acidic salts and basic salts have ions that undergo hydrolysis in aqueous
solution.
⚫The pH value of a solution depends on whether OH- or H3O+ is produced
during hydrolysis.

⚫ 3 types of salts are :

1) neutral salts
2) basic salts
3) acidic salts
 Salt Hydrolysis
MX (salt)

M+ (cation) X- (anion)

Classification of salt

Acidic salt Neutral salt Basic Salt

pH<7 pH = 7 pH>7

Strong acid Strong acid Strong base

+ + +

Weak base Strong base Weak acid

 Step 1: Balanced neutralization reaction
Acid(aq) + base(aq) → salt, MX(aq) + water(l)
or
Acid(aq) + base(aq) → salt MX(aq)

Step 2: Balanced salt dissociation equation

MX(aq) → M+(aq) + X -(aq)

Step 3: Cationic Hydrolysis produce cation (H3O+)

M+(aq) + H2O(l) ⇌ H3O+(aq) + weak base(aq)
From strong
acid

Step 4: Anionic hydrolysis produce anion, (OH-)

X-(aq) + H2O(l) ⇌ OH-(aq) + weak acid(aq)
From strong
base

Step 5: Classify the salt

Reaction Cationic Anionic Class of salt
Hydrolysis Hydrolysis
Strong acid + X X  Since hydrolysis do not occur, [H3O+] =
strong base [OH-]
 pH = 7
 Neutral salt

Strong acid + weak √ X  Since cationic hydrolysis produce H3O+

base ions
 [H3O+] > [OH-]
 pH < 7
 Acidic salt

Weak acid + strong X √  Since anionic hydrolysis produce OH- ions

base  [OH-] > [H3O+]
 pH > 7
 Basic salt

***Notes: Phases are compulsory for every equation

1) Neutral salts
Produced when strong acid reacts with strong base.

1) Neutralisation
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
strong acid strong base salt

2) Dissociation of salt
NaCl(aq) Na+(aq) + Cl-(aq)

3) Cationic hydrolysis
Na+(aq) + H2O(l) does not hydrolyzed

4) Anionic hydrolysis
54
-
5) Since hydrolysis does not occur to produce more H+ or OH-
ions,

[H+ ] = [OH-]
pH = 7
Therefore, the salt formed is a neutral salt

55
2) Basic salts
Produced when strong base reacts with weak acid.

1) Neutralisation
NaOH(aq) + HCN(aq) NaCN(aq) + H 2O(l)
strong base weak acid salt

2) Dissociation of salt
NaCN (aq) Na+(aq) + CN-(aq)

3) Cationic hydrolysis
Na+(aq) + H2O(l) does not hydrolyzed

4) Anionic hydrolysis
CN- (aq) + H O(l) HCN(aq) + OH-(aq)
56
5) Since hydrolysis produce OH- ions,

[OH-] > [H3O+]

pH > 7
Therefore, the salt formed is a basic salt

57
3) Acidic salts
Produced when strong acid reacts with weak base.

1) Neutralisation
HCl(aq) + NH3(aq) NH4Cl(aq)
strong acid weak base salt

2) Dissociation of salt
NH4Cl(aq) NH4+(aq) + Cl-(aq)

3) Cationic hydrolysis
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

4) Anionic hydrolysis
58

-
5) Since hydrolysis produce H3O+ ions,

[H3O+] > [OH-]

pH < 7
Therefore, the salt formed is a acidic salt

59
 Exercises: Classify the salt formed from reaction of acids and bases
below
1. H2SO4 and NH3

2. HNO3 and KOH

3. HCOOH and NaOH

60
 BUFFER SOLUTION
Definition:
A solution that maintains its pH when a
small amount
of strong acid or strong base is added to it.

Types of Buffer Solution

Acidic Buffer Basic Buffer

Mixture of weak acid Mixture of weak base

and its conjugate base and its conjugate acid
 ACIDIC BUFFER SOLUTION
Eg: mixture of HCN and NaCN

NaCN (contains conjugate

HCN (weak acid) base of weak acid, CN-)

Undergoes partial dissociation Undergoes complete dissociation

HCN(aq) + H2O(l) ⇌ CN-(aq) + H3O+(aq) NaCN(aq) → Na+(aq) + CN-(aq)
weak acid conj. base salt conj. base

Henderson-Hasselbalch Equation:
pH = pKa + log [conjugate base]
[weak acid]
 How acidic buffer control its pH?
Case 1 Case 2
Small amount of strong acid, H+ is added Small amount of strong base, OH- is added

CN- ion (conjugate base) reacts with H+ ion added HCN (weak acid) reacts with OH- ion added

Equation Equation
CN-(aq) + H+(aq) → HCN(aq) HCN(aq) + OH-(aq) → CN- (aq) + H2O(l)
Conj base from strong acid added Weak acid from strong base added

[CN-] decreases [CN-] increases

[HCN] increases [HCN] decreases

HCN is a weak acid which partially ionised to form H+ ion [OH-] decreases due to reaction with HCN

pH of the solution is not much affected since the change in pH of the solution is not much affected since the change in
[H+] is limited [OH-] is limited
 BASIC BUFFER SOLUTION
Eg: mixture of NH3 and NH4Cl

NH4Cl (contains conjugate

NH3 (weak base) base of weak acid, NH4+)

Undergoes partial dissociation Undergoes complete dissociation

NH3(aq) + H2O(l) ⇌ NH4+(aq) + OH-(aq) NH4Cl(aq) → NH4+ (aq) + Cl-(aq)
weak base conj. acid salt conj. acid

Henderson-Hasselbalch Equation:
pOH = pKb + log [conjugate acid]
[weak base]
 How basic buffer control its pH?
Case 1 Case 2
Small amount of strong acid, H+ is added Small amount of strong base, OH- is added

NH3 (weak base) reacts with H+ ion added HCN (weak acid) reacts with OH- ion added

Equation Equation
NH3(aq) + H+(aq) → NH4+(aq) NH4+(aq) + OH-(aq) → NH3(aq) + H2O(l)
Weak base from strong acid added Conj acid from strong base added

[NH3] decreases [NH3] increases

[NH4+] increases [NH4+] decreases

[H+] decreases due to reaction with NH3 NH3 is a weak acid which partially ionised to form OH- ion

pH of the solution is not much affected since the change in pH of the solution is not much affected since the change in
[H+] is limited [OH-] is limited
Step 1: Step 4:
Determine the mole Use Henderson-
of all species Hasselbalch
involved. equation to
calculate the pH of
a buffer solution.
Guidelines for Calculating
pH of Buffer Solution After
Addition of Strong Acid or
Strong Base
Step 2: Step 3:
Construct table in terms of Determine the
no of mole(ni, nc, nf) to molarity of all
species
determine the mole of all
involved.
species at the end of the
reaction
Example
A buffer solution is prepared by mixing 0.02 mol sodium benzoate, C6H5COONa
into 1L of 0.20 M benzoic acid, C6H5COOH.

a) Calculate the pH of the buffer solution

b) Calculate the pH of the buffer solution if
i) 0.1 mL of 1.0M HCl is added into 100mL of the buffer solution
ii) 0.1 mL of 1.0M NaOH is added into 100mL of the buffer solution
[Ka for C6H5COOH = 6.5 x 10-5]
Solution
a) pH = pKa + log [conjugate base]
[weak acid]

= pKa + log [C6H5COO-]

[C6H5COOH]

= -log (6.5 x 10-5) + log (0.02/1)

0.20
= 3.19
b) (i) C6H5COO-(aq) + H+ (aq) → C6H5COOH(aq)

n/mol C6H5COO- H+ C6H5COOH

ni MV/1000 MV/1000 MV/1000
= 0.02x100 = 1.0x0.1 = 0.2x100
1000 1000 1000
= 0.002 = 0.0001 = 0.02
nc -0.0001 -0.0001 +0.0001
nf 0.0019 0 0.0201
[C6H5COO-] = n [C6H5COOH] = n
V(L) V(L)

= 0.0019 mol = 0.0201 mol

100.1 x 10-3 L 100.1 x 10-3 L

= 0.019M = 0.201M

pH = pKa + log [conjugate base]

[weak acid]

= pKa + log [C6H5COO-]

[C6H5COOH]

= -log (6.5 x 10-5) + log (0.019)

(0.201)
= 3.16 (pH slightly decrease → more acidic)
b) (ii)
Solution : C6H5COOH (aq) + OH- (aq) → C6H5COO-(aq) + H2O(l)

n/mol C6H5COOH OH- C6H5COO-

ni 0.002 MV/1000 0.02
= 1.0x0.1
1000
= 0.0001
nc -0.0001 -0.0001 +0.0001
nf 0.0199 0 0.0021
[C6H5COO-] = n [C6H5COOH] = n
V(L) V(L)
= 0.0021 mol = 0.0199 mol
100.1 x 10-3 L 100.1 x 10-3 L
= 0.201 M = 0.199 M

pH = pKa + log [conjugate base]

[weak acid]
= pKa + log [C6H5COO-]
[C6H5COOH]
= -log (6.5 x 10-5) + log (0.021)
(0.199)
= 3.21 (pH slightly increase → less acidic)
Exercise 1

A buffer solution is prepared by mixing 400mL 1.5 M NH4Cl solution with 600
mL of 0.10 M NH3 solution.
[ Kb = 1.8 x 10-5 ]

a) Calculate the pH of buffer solution

b) Calculate the new pH of the buffer after the addition of 2.0 mL of
0.10 M HCl
c) Calculate the new pH of the buffer after the addition of 2.0 mL of
0.15 M NaOH

73
 Exercise 2
a) Calculate the pH of a 1 L buffer solution containing 1.5 M CH3COOH
and 0.20 M of CH3COONa.
pH = 3.87
b) Calculate the new pH of the buffer after the addition of 2.0 mL of 0.1 M
HCl.
pH = 3.87

c) Calculate the new pH of the buffer after the addition of 2.0 mL of 0.2 M
NaOH. [ Ka = 1.8 x 10-5 ]
pH = 3.87

74
Exercise 3
a) Calculate the pH of the solution prepared by mixing 500 mL 0.1 M
hydrazinium chloride, N2H5Cl with 500 mL 0.2 M hydrazine, N2H4.
pH = 8.53

b) Calculate the new pH of the buffer after the addition of 2.0 mL of 0.1 M HCl.
pH = 8.53

c) Calculate the new pH of the buffer after the addition of 2.0 mL of 0.2 M
NaOH . [ Kb N2H4 = 1.7 x 10-6 ]
pH = 8.54

75
7.2 ACID-BASE TITRATION
Students should be able to:
a) describe the titration process
b) distinguish between the end point and equivalence point.
c) sketch and interpret the variation of pH against titre value for
titrations between:
i) strong acid-strong base
ii) strong acid-weak base
iii) weak acid-strong base
d) identify suitable indicators for acid-base titrations
 Titration Process
Titration A laboratory technique used to
determine the concentration of an
unknown solution by using another
solution of known concentration
called standard solution
Titrant A solution of known concentration
Analyte A solution of unknown concentration
Equivalence A point where equivalent amount of
point acid and base has mixed
stoichiometrically
End point A point where indicator changes
colour
TYPES OF TITRATIONS

1. Strong acid - strong base titrations

2. Strong acid – weak base titrations
3. Weak acid – strong base titrations

78
Strong acid-strong base titration curves

* The pH starts out

low, reflecting the high
[H3O+] of the strong
acid, and increases
gradually as acid is
being neutralised by
the added base.

79
* The pH rises
sharply when the
mole of OH- that
have been added
nearly equal the
mole of H3O+ .

80
* An additional drop or two of
base neutralises the
final tiny excess of acid and
introduces a tiny excess of base,
so pH jumps 6 to 8 unit.

* Beyond this sharp portion, the

pH increases slowly again as
more base is added.

81
 Weak acid-strong base titration curves

* The initial pH is higher

than strong acid-strong
base titration curve
because the weak acid
dissociates only slightly,
less H3O+ is present.

82
* A gradually rising
portion of the curve,
called the buffer region,
appears before the
sharp rise to the
equivalence point.

83
* The pH at the
equivalence point >
7.0.
The solution contains
the basic salt.

84
 Weak base-strong acid titration curves

* The pH starts above 7.0

(~11) because the weak
base dissociates only
slightly.

* The pH decreases
gradually in the buffer
region.

85
* After the buffer region,
the curve drops
vertically to the
equivalence point.

* Beyond the equivalence

point, the pH decreases
slowly as excess H3O+ is
added.
86
 Titration curve between strong acid & strong
base (equivalence point =7)
NaOH Suitable indicator: Bromothymol blue
Equivalence pH range: 6.0-7.6
titrant
point
Colour change: Yellow to blue

HCl
analyte

Titration curve between strong acid & weak NH3 titrant

Equivalence
base (equivalence point < 7) point
Suitable indicator: Methyl red
pH range: 4.4-5.2
Colour change: Red to yellow HCl
analyte

Equivalence NaOH
point titrant
Titration curve between weak acid & strong
base (equivalence point > 7)
Suitable indicator: Phenolphthalein
CH3COOH
pH range: 8.3-10.0
analyte
Colour change: Colourless to pink
How to sketch a titration curve
Steps :
1. Calculate the initial pH of the solution
- identify the analyte (solution in the conical
flask). Whether strong acid, weak acid,
strong base or weak base.

2. Determine the equivalence point :

- Volume and pH
88
3. pH jump (steep portion / sharp portion)
- depends on the type of the titration
Type pH jump

Strong acid-strong base 3-11

Strong acid-weak base 3-7

Weak acid-strong base 7-11

4. Identify the final pH

- depends on the [ ] of the titrant (solution in
the burette). 89
 FFind moles of acid and base

Determine which is used up(reactant with fewer moles)

mols?

Subtract the smaller mole value from both the acid and base amount

If mole of acid left over If mole of base left If mole of acid = mole of base
over

Calculate molarity of acid. Calculate molarity of base pH = 7.0

M = nacid / V/total
mol L(L) M = nbasemol / L(L)L
/ Vtotal
(Vtotal = Vacid + Vbase) (Vtotal = Vacid + Vbase)

Find pH using Find pOH using

pH = -log [H+] pH = -log [OH-]
Then, find pH
pH = 14-pOH
Example :
A 25.00 mL sample of 0.10 M HCl is titrated with 0.1M NaOH.
Calculate the pH of the solution

i. before the addition of NaOH

ii. after the addition of 10.0 mL of NaOH
iii. at the equivalence point
iv. after the addition of 35.0 mL of NaOH
v. sketch the titration curve
Solution :
i. pH before the addition of 0.10 M NaOH

Dissociation equation of HCl (strong acid) :

HCl(aq) H+(aq) + Cl-(aq)

0.10 M 0.10 M 0.10 M

pH = -log[H+]
= -log(0.1)
= 1.0
ii. pH after the addition of 10.0 mL of 0.10 M NaOH

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

n/mol HCl NaOH NaCl
ni MV/1000 MV/1000 0
= 0.1x25 = 0.1x10
1000 1000
= 0.0025 = 0.001

The pHnc solution is -0.001

calculated from-0.001 +0.001
the amount of
HCl left
nf after partial neutralization. 0
0.0015 0.001

[HCl] = [H ] = 0.0015mol
+ pH = -log [H+]
(25+10) x 10-3 L = -log (0.043)
= 0.043 M = 1.37
iii. At the equivalence point

moles of H+ = moles of OH-

[H+] = [OH-] = 1x10-7 M
pH = 7

****To sketch titration curve, we have to find the pH and volume of titrant added at
equivalence point
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

MaVa = a
MbVb b

25 x 0.1 = 1
0.1 x Vb 1

Vb = VNaOH = 25 mL
iv. pH after the addition of 35.0 mL of 0.10 M NaOH

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

n/mol HCl NaOH NaCl
ni MV/1000 MV/1000 0
= 0.1x25 = 0.1x35
1000 1000
= 0.0025 = 0.0035
nc -0.0025 -0.0025 +0.0025
The pH
n solution is calculated
0 from0.001
the amount of0.0025
f

pOH = -log [OH-]

[NaOH] = [OH-] = 0.001mol
= -log (0.0167)
(35+25) x 10-3 L
= 1.78
= 0.0167 M
pH = 14-1.78
= 12.2
v. The titration curve for strong acid-strong base titration
NaOH (mL) 0 10 25 35
pH 1.0 1.37 7 12.2

pH
14
12
10
8
Equivalence point =7
6
4
2
0
VNaOH (mL)
0 10 20 25 30 40 50
Exercise :
A 30.00 mL sample of 0.5 M HCl is added dropwise to 25.00
mL of 0.5 M NaOH. Calculate the pH of the solution
i. before the addition of HCl
ii. after the addition of 10.0 mL of HCl
iii. at the equivalence point
iv. after the addition of 30.0 mL of HCl
v. sketch the titration curve
 Acid-base Indicator
Used to indicate the end point of an acid-base titration by its colour
Indicator pH range change. Colour
Acidic Basic

Thymol blue 1.2-2.8 Red Yellow

Bromophenol blue 3.0-4.4 Yellow Purple
Methyl orange 3.1-4.4 Red Yellow
Methyl red 4.4-6.2 Red Yellow
Bromothymol blue 6.0-7.6 Yellow Blue
Cresol red 7.2-8.8 Yellow Red
Phenolphthalein 8.3-10.0 Colourless Pink
Alizarin yellow 10.0-12.0 Yellow Red
Exercise 1
The pH range and the colour change for 3 indicator X, Y and Z is shown in
the table below. Determine X, Y and Z.

Indicator pH range colour change

X 1.2 – 2.8 Red → Yellow

Y 6.0 – 7.6 Yellow → Blue

Z 8.3 – 10.0 Colourless → Yellow

7.3 SOLUBILITY EQUILIBRIA
Students should be able to:
a) define solubility, molar solubility and solubility product, K SP .
b) calculate KSP from concentrations of ions and vice versa.
c) predict the possibility of precipitation of slightly soluble ionic
compunds by comparing values of ion-product, Q to KSP .
d) define and explain the common ion effect.
e) perform calculations related to common ion effect.
 DEFINITION

1) Solubility 2) Molar Solubility

Maximum amount of solute Number of moles of solute

dissolved in 1L of saturated dissolved in 1L (or 1 dm3) of
solution saturated solution
Unit: g/L or mol/L Unit: mol/L @mol/ dm3

g/L ÷  molar mass mol/L

x  molar mass
Solubility Product, KSP
 Soluble salt such NaCl and KNO3 has an extremely high value of Ksp .

 The smaller the value of Ksp the less soluble the compound in water.

 Higher temperature = higher solubility = larger K sp value

If K value is given, means the ionic compound is in solid

sp
phase. The dissociation equation of solid ionic compound

use arrow and form aqueous cation and anion.

103
Guidelines for Calculating Solubility Product, KSP From
Concentration of Ions

STEP 1 STEP 2 STEP 3

If a solubility of Write balanced Calculate the
ionic compound is equation (phases solubility product,
given in g/L, convert are compulsory) and KSP. Unit of KSP is
it into molar construct ICE table negligible.
solubility (mol/L). to determine the
equilibrium
concentration of
cation and anion.
x x x
x x
 Guidelines for Calculating Concentration of Ions From
Solubility Product, KSP
STEP 1 STEP 2 STEP 3
Write balanced Calculate the molar If necessary, convert
equation & solubility(mol/L) of molar solubility
construct ICE table ionic compound. (mol/L) to g/L
to determine the (represented by x)
equilibrium
concentration of
cation and anion.
 (aq) (aq)
(s)

/L Ag2SO4
 Exercise 1

Write the solubility product expression and state the units of K sp

for each of the following ionic compounds.

a) Ca3(PO4)2 b) Ag2CO3

108
 Exercise 2

The solubility product of silver chromate(VI), Ag2CrO4 is 2.4

x10-12 mol3dm-9. Calculate the concentration of Ag+(aq) and
CrO42-(aq) in the saturated solution.

Ans: [Ag+] = 1.68 x 10-5 M

[CrO42-] = 8.43 x 10-5 M

109
 Exercise 3

The solubility of silver sulphide, Ag2S is 5.0x10-17.

Calculate the solubility product of Ag2S.

Ans: 5.0 x 10-49

110
 Exercise 4

Calculate the solubility of copper (II) hydroxide, Cu(OH)2, in

g L-1.

Ksp Cu(OH)2 = 2 x 10-20 M3,

Mr Cu(OH)2 = 97.57g mol-1
 Predicting the Possibility of Precipitation of Slightly
Soluble Ionic Compounds by Comparing the Values of
Ion-Product, Q with Solubility Product, KSP
PbCl2 (s) ⇌ Pb2+(aq) + 2Cl-(aq)

Q = [Pb2+] [Cl-]2

If Q < KSP Low concentration of soluble ions in the solution.

Solution is unsaturated.
No precipite formed.
If Q = KSP Solution is just saturated with its soluble ions.
No precipite formed.
If Q > KSP High concentration of soluble ions in the solution.
Solution is supersaturated.
Precipite formed.
 Example

Exactly 50 mL of 0.1 M Ba(OH) are added to 50 mL of 0.5 M Na SO . Will a precipitate form?

2 2 4

(K BaSO = 1.1x10-10 )
sp 4

Solution:

No of moles of Ba(OH) = MV = 0.1 x 0.05 = 0.005 mol

2

No of moles of Na SO = MV = 0.5 x 0.05 = 0.0255 mol

2 4

V total = 50 + 50 = 100 mL = 0.1 L

113
Ba(OH) (aq) → Ba2+(aq) + 2OH-(aq)
2
[ ]/M Ba(OH)2 Ba2+ OH-
Initial 0.005mol 0 0
0.1 L
= 0.05
Change -0.05 +0.05 + 2(0.05)
final 0 0.05 0.1

Na SO (aq) → 2Na+(aq) + SO 2-(aq)

2 4 4
[ ]/M Na2SO4 Na+ SO42-
Initial 0.025mol 0 [ ]/M
0
0.1L [ ]/M
= 0.25
Ba(OH)
2
Change -0.25 +2(0.25)
Ba2+
+0.25
Final 0 0.5 0.25
Ba(OH)
2

114
BaSO (s) ⇌ Ba2+(aq) + SO 2-(aq)
Q = [Ba2+] [SO42- ]
= 0.05 x 0.25
= 0.0125

Since Q is larger than KSP (1.1 x 10 -10 )

The solution is supersaturated
Precipitate is formed.
 Exercise 1

Will precipitate form when 50 mL 0.001 M NaOH is added to

150 mL of 0.01 M MgCl2.
(Ksp Mg(OH)2 = 2 x 10-11)

116
 Exercise 2

Exactly 200 mL of 0.0040 M AgNO3 are added to 800

mL of 0.008 M K2SO4. Will a precipitate form?
(Ksp Ag2SO4 = 1.4x10-5 M3)

117
 THE EFFECT OF COMMON ION ON
SOLUBILITY

Common Ion Common Ion Effect

An ion that is common to two or Decrease the solubility of slightly

more components in a mixture of soluble ionic compound due to the
solution of ions. presence of common ion.
 Solubility of PbCl2

In pure water In KCl solution

(Common ion effect :Cl-)

Molar solubility is x mol/L Molar solubility < x mol/L

PbCl 2(s) ⇌ Pb2+ (aq) + 2Cl-(aq) PbCl2(s) ⇌ Pb2+ (aq) + 2Cl-(aq)

KCl(aq) → K+ (aq) + Cl-(aq)

The addition of KCl increases

the concentration of Cl- ion
(common ion) in the solution

According to Le Chatelier’s
principle, equilibrium shift to
the left.

[PbCl2] increase

Thus, solubility of PbCl2

decrease
 Example

The solubility product for CaF is 4.0 x 10-11. Calculate the molar solubility of CaF
2 2

a) in pure water

b) in 0.05 M KF solution

c) compare the solubility of CaF

2
in pure water and in KF solution

120
Solution:

a) Let x = molar solubility of CaF

2
in pure water

CaF (s) ⇌ Ca2+(aq) + 2F-(aq)

2
[ ]/M Ca2+ F-
Initial 0 0
Change +x +2x
Equilibrium x 2x

K = [Ca2+] [F- ]2
SP
4.0 x 10-11 = (x) (2x)2

x = 2.15 x 10-4 M 121

b) Let y = molar solubility of CaF2 in 0.05 M KF solution.
KF(aq) → K+(aq) + F-(aq)
0.05M 0.05 M
CaF2(s) ⇌ Ca2+(aq) + 2F-(aq)
[ ]/M Ca2+ F-
Initial 0 0.05
Change +y +2y
Equilibrium y 0.05 + 2y

KSP = [Ca2+] [F- ] 2

4.0 x 10-11 = (y) (0.05 +2y) 2

Assume y is very small, 0.05 +2y ≈ 0.05

4.0 x 10-11 = (y) (0.05) 2
y = 1.6 x 10-8 M
c) solubility of CaF in KF solution is lower (smaller K value) than in pure water because the presence of
2 SP
common ion, F- decreases the solubility of CaF in KF solution.
2

123
 Exercise 1

Calculate the solubility of AgCl (mol L-1) in :

a. liquid water
b. 0.05 M of silver nitrate solution.
(Ksp AgCl = 1.6 x 10-10)
c. compare the solubility of AgCl in liquid water and silver
nitrate solution.
124