Chapter 7.

0 : IONIC
EQUILIBRIA

7.2 :
ACID‒BASE
TITRATIONS

Chemistry Unit, Kolej Matrikulasi Johor

 Equivalent
Titration point
process End point

Sketch & interpret

Acid Base curve
Titrations

Weak Acid & Strong Base

Strong Acid & Weak Base
Suitable
Indicators
 TITRATION
A method for determining the
concentration of a solution using another
solution (known concentration), called
standard solution.
 Burette:
EXAMPLE: NaOH(aq) - titrant

Indicator:
EXAMPLE:
phenolphthalein

Conical flask:
EXAMPLE: CH3COOH(aq) - analyte
 EQUIVALENCE POINT
The point at which the reaction is complete

The number of moles of base is stoichiometrically

to the number of moles of acid have reacted

EXAMPLE:
HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
0.1 mol 0.1 mol

H2SO4(aq) + 2NaOH(aq)  Na2SO4(aq) + H2O(l)

0.1 mol 0.2 mol

No more acid or base left in the solution

 END–POINT
The point at which the indicator change color

The titration is stopped at the end point

The end point should occur at the equivalence point.

Therefore, selecting suitable indicator with an end
point close to equivalence point is essential to obtain
the ideal result in titration
 INDICATOR
• Weak organic acid that has different colour than its
conjugate base

• Commonly used to indicate the equivalence point of

an acid-base titration by its colour change.

• Acid-base indicators has its own pH range in which

the colour change occurs
 pH RANGE
Range over which the indicator changes
from the acid color to the base color

EXAMPLE:
pH range

Phenolphthalein 8.3 ~ 10.0

Methyl orange 3.1 ~ 4.4

Methyl red 4.2 ~ 6.3

 The pH range at the equivalence point is

determined from the steep vertical portion in the
titration curve
 ACID-BASE TITRATION CURVE

• A plot of the pH of a solution of acid

(or base) versus the volume of base
(or acid) added to the solution.
 TYPES OF THE TITRATION
CURVE

• Strong Acid – Strong Base

• Weak Acid – Strong Base
• Strong Acid – Weak Base
 The Titration of a Strong Acid with a Strong Base

Titration of 25.0 mL of 0.100 M HCl with 0.100 M NaOH

a) Initial pH (before adding any base)

The initial pH of the
solution is simply the pH
of a 0.100 M HCl solution.

Since HCl is a strong

acid, the concentration
of H3O+ is also 0.100 M
and the pH is 1.00

pH = -log [ H3O+]

pH = -log (0.100)
pH = 1.00
 b) pH after adding 5.00 mL NaOH

As NaOH is added to the solution, it neutralizes H3O+ :

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

 find moles of H3O+ remaining

HCl NaOH
Initial mol = 0.10 mol / L = 0.10 mol / L
x 0.025 L x 0.005 L
= 0.0025 = 0.0005
Change (mol) – 0.0005 – 0.0005
Remaining
0.002 0
(mol)
Total volume = 25 mL + 5 mL
= 30 mL
= 0.030 L

Mole of remaining HCl

[HCl] =
Total volume of solution (in L)
0.002 mol
=
0.030 L
= 0.0667 M
 HCl(aq) + H2O(l)  H3O+(aq) + Cl–(aq)
0.0667 M 0.0667 M

pH = – log [H3O+]

= – log (0.0667)
= 1.18
c) pH’s after adding 10.0, 15.0 and 20.0 mL NaOH

As more NaOH is added, it further neutralizes the H3O+ in

the solution. The pH at each point is calculated in the same
way that we calculated the pH at the 5.00 mL point.

Volume of pH
NaOH added
(mL)
10.0 1.37
15.0 1.60
20.0 1.95
c) pH after adding 25.0 mL NaOH ( Equivalence point)

At the equivalence point, the strong base has completely

neutralized the strong acid. The solution contain salt and
water
 find pH of the salt solution

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

HCl NaOH
Mole
= 0.10 mol / L = 0.10 mol / L
x 0.025 L x 0.025 L
= 0.0025 = 0.0025

Change (mol) – 0.0025 – 0.0025

Remaining 0 0
(mol)
 HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
0.0025 mol 0.0025 mol

0.0025 mol of NaOH reacted with 0.0025 mol of HCl

 no more HCl and NaOH

Solution contains Na+ and Cl–

 Na+ and Cl– do not hydrolysed

The pH at equivalence point is calculated based on
[H3O+] from the autoionization of water.

The [H3O+] from the autoionization of water is

1.00 x 10-7 M

[H3O+] = 1.0 x 10–7

pH = 7.00 (neutral)
d) pH after adding 30.0 mL NaOH

After equivalence point:

 Find moles of OH– remaining

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

HCl NaOH
Mole = 0.10 mol / L = 0.10 mol / L
x 0.025 L x 0.030 L
= 0.0025 = 0.0030

Change (mol) – 0.0025 – 0.0025

Remaining
0 = 0.0005
(mol)
Total Volume = 25 mL + 30 mL = 0.055 L

[NaOH] = Mole of NaOH remaining

Total volume (in L)
0.0005 mol
=
0.055 L
= 0.00909 M

NaOH(aq)  Na+(aq) + OH–(aq)

0.00909 M 0.00909 M
 pOH = – log [OH–]

= – log (0.00909)

= 2.04

pH + pOH = pKw = 14.00

pH = pKw – pOH

= 14.00 – 2.04

= 11.96
 e) After adding 40.00 mL NaOH

After equivalence point:

 Find moles of OH– remaining

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

HCl NaOH
Mole = 0.10 mol / L = 0.10 mol / L
x 0.025 L x 0.040 L
= 0.0025 = 0.0040

Change (mol) – 0.0025 – 0.0025

Remaining
0 = 0.0015
(mol)
Total Volume = 25 mL + 40 mL = 0.065 L

[NaOH] = Mole of NaOH remaining

Total volume (in L)
0.0015 mol
=
0.065 L
= 0.02308 M

NaOH(aq)  Na+(aq) + OH–(aq)

0.02308 M 0.02308 M
 pOH = – log [OH–]

= – log (0.02308)

= 1.64

pH + pOH = pKw = 14.00

pH = pKw – pOH

= 14.00 – 1.64

= 12.36
As NaOH is added beyond the equivalence point, it
becomes the excess reagent. The [OH-] remaining
after neutralization is calculated.
STRONG ACID & STRONG BASE
TITRATION CURVE
 Titration curve: pH versus volume NaOH
pH

14.00
13.00
12.00
11.00
After equivalence point
10.00 (OH- in excess)
9.00
8.00
7.00 Equivalence point
6.00 pH = 7.00
5.00
Before equivalence
4.00
point
3.00 (H3O+ in excess)
2.00
1.00

0 25 50
Initial pH Volume of NaoH added (mL)
 Initial pH
•The pH of the solution
before the addition of any
base is determined by the
initial concentration of the
strong acid.

•The pH starts out low,

reflecting the high [H3O+]
Initial pH
of the strong acid
 Between initial pH
and equivalence
point
• As NaOH is added, the pH
increases gradually as
acid is being neutralised
by the added base.

•The pH before equivalence

point is determined by the
[H3O+] not yet neutralised.
• The pH rises sharply
when the mole of OH-
added nearly equal to
the mole of H3O+
 pH at equivalence point

• At the equivalencene
point, the number of moles
of base added is
stoichiometrically to
the number of moles acid
have reacted
• The solution consists of
salt and water

• Neither reactant is in
excess and the pH = 7.00
 After equivalence point
• After the equivalence
point, OH- is in excess.
The pH of the solution is
determined by the
concentration of excess
base in the solution.

• The pH increases slowly

again as more base is
added
 pH range
Phenolphthalein 8.3 ~ 10.0

Methyl red 4.2 ~ 6.3

Methyl red Either methyl red or phenolphthalein is

a suitable indicator because each
changes color on the sharp increased of
Volume of NaOH added (mL) the curve

Equivalence point
pH = 7.00

Phenolphtalein

Volume of NaOH added (mL)

 pH range
Phenolphthalein 8.3 ~ 10.0

Methyl red 4.2 ~ 6.3

Methyl Either methyl red or

red phenolphthalein is
Volume of NaOH added (mL) a suitable indicator
because each changes
color on the sharp
increased of the curve

Equivalence point
pH = 7.00

Phenolphtalein
Volume of NaOH added (mL)
Suitable indicators for strong acid-strong base titration are :

Reason :
The indicators above are suitable because the pH
range of indicators (the colour change) fall within the
pH at the equivalent point of the titration.
pH = 10 pH = 5 pH = 2

METHYL RED
Equivalence point detected using phenophtalein
 EXERCISE 1 :

Sketch the titration curve when :

a) 5.00 mL
b) 10.00 mL
c) 15.00 mL
d) 24.90 mL
e) 25.00 mL
f) 25.10 mL
g) 30.00 mL
h) 45.00 ml
0.100 M HNO3 is added to 25 mL 0.100 M NaOH
 The Titration of weak acid and strong base

Titration of 25.0 mL of 0.100 M CH3COOH with

0.100 M NaOH.

a) Initial pH (before adding any base)

The initial pH of the solution is the pH of a

0.100 M CH3COOH solution.

Since CH3COOH is a weak acid,

the concentration of H3O+and the
pH are calculated from the
incomplete dissociation in
aqueous solution

Ka CH3COOH = 1.8 x 10-5 39

 H2O(l) + CH3COOH(aq) H3O+(aq) + CH3COO–(aq)
[ ]i –
0.100 0 0
[ ]∆
– –x +x
+x
[ ]eq
– 0.100 – x x x

[H3O+][CH3COO–]
Ka = x2
= = 1.8 x 10-5
[CH3COOH] 0.100 – x
 x2
Ka =
0.100 – x
Ka << 1  assume x very small

Assumption: 0.100 – x  0.100

x2
Ka = = 1.8 x 10–5
0.100

x = 1.34 x 10-3 M
 [H3O+] = x = 1.34 x 10-3 M

pH = – log [H3O+]

= – log (1.34 x 10-3 )

= 2.82

The pH is initially at a higher values (less acidic) than it

is for a strong acid of the same concentration
b) pH after adding 5.00 mL NaOH

The solution contains excess weak acid and its salt.

Thus, the solution contains a mixture of CH3COOH and
CH3COO– (buffer solution).

Determination of the pH involves two steps :

• consider the neutralisation reaction between CH3COOH

and OH- to determine [CH3COOH] and [CH3COO–].

• calculate the pH of this buffer pair

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

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

ni 0.0025 0.0005 0 -

n∆ – 0.0005 – 0.0005 + 0.0005 -

nf 0.0020 0 0.0005 -

[CH3COO–]
pH = pKa + log
[CH3COOH]
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of NaoH added (mL)
Total Volume = 25 mL + 5 mL = 30 mL = 0.030 L

[CH3COO–] = 0.0005 mol

= 0.0167 M
0.030 L

0.0020 mol = 0.00667 M

[CH3COOH] =
0.030 L

pH = -log (1.8 x 10-5) + log 0.0167

0.00667

= 4.15
d) pH after adding 10.0, 15.0 and 20.0 mL NaOH

As more NaOH is added, it converts more CH3COOH into

CH3COO-.

The pH of buffer solution is calculated by using

Handerson-Hasselbalch equation

Volume of Mol of Mol of pH

NaOH CH3COO- CH3COOH
added (mL)

10.0 0.001 0.0015 4.58

15.0 0.0015 0.001 4.93
20.0 0.0020 0.0005 5.35
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of NaoH added (mL)
c) pH after adding 25.0 mL NaOH ( Equivalence point)

At the equivalence point, 0.0025 mol of NaOH have been

added and therefore all of the CH3COOH has been
converted into its conjugate base, CH3COO– .

No more CH3COOH and NaOH left. Thus, the solution

contains CH3COONa (salt) and water.

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

0.0025 mol 0.0025 mol 0.0025 mol

 The salt will dissociate :

CH3COONa(aq)  CH3COO-(aq) + Na+ (aq)

The conjugate base undergoes hydrolysis :

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

Since the OH- formed in the hydrolysis process, the salt

formed is a basic salt at equivalence point ( pH >
7.00 ).
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of NaoH added (mL)
d) pH after adding 30.0 mL NaOH
At this point in the titration, 0.0030 mol of OH– have been
added. NaOH has thus become the excess reagent.
CH3COOH(aq) + OH-(aq)  CH3COO–(aq) + H2O(l)
ni 0.0025 0.003 0 -

n∆ – 0.0025 – 0.0025 + 0.0025 -

nf 0 0.0005 0.0025 -

The solution is now a mixture of a strong base

(NaOH) and a weak base (CH3COO–)
In this region, [OH-] from the reaction of CH3COO- with
water is negligible relative to [OH-] from the excess NaOH.
Thus, the pH is determined by the concentration of OH-
from the excess NaOH.

Total Volume = 25 mL + 30 mL = 55 mL = 0.055 L

[OH–] = 0.0005 mol = 0.0091 M

0.055 L
pOH = – log [OH–]

= – log (0.0091)

= 2.04

pH = pKw – pOH

= 14.00 – 2.04

=11.96
e) After adding 35.0, 40.0 and 50.0 mL NaOH

As more NaOH is added, the basicity of the

solution increases further. The OH- in the solution
is in excess. The pH is determined by the
concentration of OH-

Volume of pH
NaOH
added (mL)

35.0 12.22
40.0 12.37
50.0 12.52
WEAK ACID & STRONG BASE
TITRATION CURVE
 Titration curve: pH versus volume of NaOH
pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00 Equivalence point
6.00 pH > 7.00
5.00 (weak conjugate base)
4.00
3.00
2.00
1.00

0 25 50
Volume of NaoH added (mL)
 Initial pH

The initial pH is higher than

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

Initial pH
 Between initial pH
and equivalence
point

A gradually rising portion of

the curve, called the buffer
region, appears before the
sharp rise to the equivalence
point.
 pH at equivalence point

The pH at the equivalence

point > 7.00
The solution contains the
basic salt.
 pH after equivalence point

The solution is now contains

mixture of strong base and
weak base.

The strong base completely

overwhelms the weak base

The pH is determined by the

concentration of OH- from
excess strong base
 pH range
Phenolphthalein 8.3 ~ 10.0

Methyl red 4.2 ~ 6.3

Phenolphthalein is a suitable indicator

because it changes color on the steep portion
of the curve, but methyl red is not its color
changes over a large volume range
 The Titration of weak base and strong acid

EXAMPLE: 25 mL 0.100 M NH3(aq) in conical flask

0.100 M HCl(aq) in burette

a) Initial pH (before adding any acid)

The initial pH of the solution is the pH 0.100 M of NH3 .

Since NH3 is a weak base,

the concentration of H3O+and the pH are
calculated from the incomplete dissociation in
aqueous solution
Kb NH3 = 1.8 x 10-5
 H2O(l) + NH3(aq) OH-(aq) + NH4+(aq)
[ ]i –
0.100 0 0
[ ]∆
– –x +x
+x
[ ]eq
– 0.100 – x x x

[OH-][NH4+]
Kb = x2
= = 1.8 x 10-5
[NH3] 0.100 – x
 x2
Kb =
0.100 – x
Kb << 1  assume x very small

Assumption: 0.100 – x  0.100 (x negligible)

x2
Ka = = 1.8 x 10–5
0.100

x = 1.34 x 10-3 M
[OH-] = x = 1.34 x 10-3 M

pOH = – log [OH-]

= – log (1.34 x 10-3 )

= 2.82

pH + pOH = pKw = 14.00

pH = pKw – pOH

= 14.00 – 2.82

= 11.18
b) pH after adding 5.00 mL HCl

The added HCl converts a stoichiometric amount of the

base into its conjugate acid. Thus, the solution contains a
mixture of NH3 and NH4+ (buffer solution).

Determination of the pH involves two steps :

• consider the neutralisation reaction between NH3

and HCl to determine [NH3] and [NH4+].

• calculate the pH of this buffer pair

 NH3(aq) + HCl(aq)  NH4Cl(aq) + H2O(l)

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

ni 0.0025 0
0.0005 -

n∆ – 0.0005 – 0.0005 + 0.0005 -

nf 0.0020 0 0.0005 -

[ NH4+]
pOH = pKb + log
[ NH3]
Total Volume = 25 mL + 5 mL = 30 mL = 0.030 L

[NH4+] = 0.0005 mol

= 0.0167 M
0.030 L

0.0020 mol = 0.00667 M

[NH3] =
0.030 L
0.0167
pOH = -log (1.8 x 10-5) + log
0.00667
= 4.35

pH = 14.00 – 4.35
= 9.65
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of HCl added (mL)
d) pH after adding 10.0, 15.0 and 20.0 mL HCl

As more HCl is added, it converts more NH3 into

NH4+The solution is now a buffer.

The pH of buffer solution is calculated by using

Henderson-Hasselbalch equation

Volume of Mol of Mol of pH

HCl added NH4+ NH3
(mL)

10.0 0.001 0.005 9.43

15.0 0.005 0.001 9.07
20.0 0.002 0.0005 8.65
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of HCl added (mL)
c) pH after adding 25.0 mL HCl ( Equivalence
point)
At the equivalence point, 0.0025 mol of HCl have been
added and therefore all of the NH3 has been converted into
its conjugate acid, NH4+.

No more NH3 and HCl left. Thus, the solution contains

NH4Cl (salt) and water.

NH3(aq) + HCl(aq)  NH4Cl(aq) + H2O(l)

0.0025 mol 0.0025 mol 0.0025 mol

The salt will dissociate :

NH4Cl(aq)  NH4+(aq) + Cl- (aq)

The conjugate base undergoes hydrolysis :

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

Since the H3O+ is formed in the hydrolysis process,

the salt formed is an acidic salt at equivalence point
( pH < 7.00 ).
 pH

14.00
13.00
12.00
11.00
10.00
9.00
8.00
7.00
6.00
5.00
4.00
3.00
2.00
1.00

0 25 50
Volume of HCl added (mL)
d) pH after adding 30.0 mL HCl
At this point in the titration, 0.0030 mol of H3O+ have been
added. HCl has thus become the excess reagent.
NH3(aq) + H3O+(aq)  NH4+aq) + H2O(l)
ni 0.0025 0.003 0 -

n∆ – 0.0025 – 0.0025 + 0.0025 -

nf 0 0.0005 0.0025 -

The solution is now a mixture of a strong acid (HCl)

and a weak acid (NH4+)
In this region, [H3O+] from the reaction of NH4+ with water is
negligible relative to [H3O+] from the excess HCl. Thus, the
pH is determined by the concentration of H3O+ from the
excess HCl.

Total Volume = 25 mL + 30 mL = 55 mL = 0.055 L

0.0005 mol
[H3O+] = = 0.0091 M
0.055 L
pH = – log [H3O+]

= – log (0.0091)
= 2.04
[OH-] = 1 x 10-14

0.0091 M

[OH-] = 1.1 x 10-12 M

pOH = – log [OH-]

= – log (1.1 x 10-12 )

= 11.96

pH = 14.00 – 11.96
= 2.04
e) After adding 35.0, 40.0 and 50.0 mL HCl

As more HCl is added, the acidity of the solution

increases further. H3O+ in the solution is in
excess. The pH is determined by the
concentration of H3O+ from HCl

Volume of pH
HCl added
(mL)

35.0 0.0167
40.0 0.023
50.0 0.033
WEAK BASE & STRONG ACID
TITRATION CURVE
 Titration curve: pH versus volume HCl
pH

14.00
13.00
12.00 Before equivalence point
11.00 (buffer region)
10.00
9.00
8.00
7.00 Equivalence point
6.00 pH < 7.00
5.00 (weak conjugate acid)
4.00 After equivalence
3.00 point
2.00
1.00

0 25 50
Volume of HCl added (mL)
 Initial pH
The pH starts above
Initial pH 7.0 (~11) because the
weak base dissociates
only slightly.
 pH between initial
and equivalence
point

The pH decreases
gradually in the buffer
region.
 pH at equivalence point

After the buffer region, the

curve drops vertically to the
Equivalence point
pH < 7.00 equivalence point.
(weak conjugate acid)
The pH at equivalence point
is < 7.00

.
 pH after equivalence point

Beyond the equivalence

point, the pH decreases
slowly as excess H3O+ is
added.
 pH range
Phenolphthalein 8.3 ~ 10.0

Methyl red 4.2 ~ 6.3

Methyl red is a suitable indicator because it

changes color on the steep portion of the curve,
but phenolphathalein is not its color changes
over a large volume range
 How to determine the suitable indicator for
titrations
 Choose an indicator which the endpoint pH range lies
on the steep portion of the titration curve.
 This choice ensures that the pH at the equivalent point
will fall within the range over which indicator changes
color.

Types of Titrations pH jump Suitable Indicators

Strong Acid-Strong Base 3 – 11 Any Indicator except thymol blue

Weak Acid-Strong Base 7 – 11 Phenolphthalein, cresol red

Strong Acid-weak Base 3–7 Methyl orange, methyl red, chlorophenol

blue, bromophenol blue
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

90
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 concentration of the titrant (solution
in the burette).
91
 EXERCISE 2 :

Sketch the titration curve of 25 mL 0.2 M HCl and

0.1 M NH3.

92
END OF SLIDE SHOW