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

The strength of an acid is measured by the ease with which it donates a proton while that of a
base is measured by the ease with which it accepts protons

THE IONIC PRODUCT OF WATER

Pure H2O has a very slight conductivity due to its slight dissociation
H2O(l) H+(aq) + ŌH(aq)
Applying the equilibrium law
K= [H+] [ŌH]
[H2O]
Since the degree of dissociation of H2O molecules is very small, concentration of water is taken
to be a constant so that
Kw = [H+] [ŌH]
Kw is called ionic product of water.

It’s equal to 1 ×10-14 mol2l-2 or mol2dm-6 at 250C

[H+] = [OH] = 1 × 10-7 mol l-1
H2O(l) H+(aq) + ŌH(aq) H= +ve

Increase in temperature shifts equilibrium to the right in order to absorb the added heat and
restore the original equilibrium. The concentration of ŌH and H+ increases and the Kw increases.
Thus Kw increases with increase in temperature.

Hydrogen ion concentration and PH

The PH of a solution is the logarithm to base ten of the reciprocal of the H+ concentration
1
PH= log10 [𝐻 +]

PH= − log10 [𝐻 + ]

It is a measure of the [H+]

Consider the ionization of water
H2O(l) H+(aq) + ŌH(aq)
Pure water can be considered as an acid at 250C
It contains 1 × 10-7 moll-1 of H+ ions
[H+] = 1 × 10-7
Therefore PH = - log10 [H+]
= - log10(1×10-7)
=7
At 50 C, Kw = 5.47 ×10-14 mol2l-2
0

125
 Kw = [H+] [OH]
[H+] = 2.34 × 10-7 mol l-1
 PH= - log (2.34 ×10-7)
= 6.63
Thus as temperature increase, the PH of H2O decreases and its acidity increases.
NOTE
i) The PH of H2O also decreases when left standing in air. This is because it absorbs
CO2 from the atmosphere to form weak carbonic acid.
H2O(l) + CO2(g) H2CO3(aq) 2H+(aq) + CO32-(aq)

PH OF ACIDS
Calculate the PH of 0.01M HCl solution since the acid is completely ionized [H+] = [HCl]
= 0.01
Therefore PH = - log (0.01)
=2
With a more concentrated solution, the PH can be calculated if the concentration and degree of
ionization of the acid are known. The degree of ionization of a 4M solution if HCl is 0.45. Thus
of the 4 moles the number of moles dissociated is 4 × 0.45 = 1.8 moles
[H+] = 0.45 × 4
= 1.8
PH = - log (1.8)
= - 0.255
Thus for an incompletely dissociated acid
[H+] = C𝛼
Where C is concentration
𝛼 is the degree of dissociation
For weak acids the [H+] can also be determined, from the concentration and dissociation constant
Ka.
Consider the ionization of a weak acid HA. If C is the initial concentration of the acid and alpha
is the degree of dissociation.
HA(aq) H+(g) + A-(aq)
Ka= [H+] [A-]
[HA]

Since [H+] = [A-] Ka= [H+]2

[HA]
Ka = [H+]2
C
+ 2
[H ] = KaC

126
  [H+] = √𝐾𝑎 𝐶 …………………………….. (1)

But [H+] = C𝛼

 C𝛼 = √𝐾𝑎 𝐶

And 𝐶 2 𝛼 2 = 𝐾𝑎 𝐶
𝐾𝑎 𝐶
𝛼2 =
𝐶2
𝐾𝑎
𝛼= √ …………………………………… (2)
𝐶
Then
(1)2 ∙ (2)2
𝐾
[H+]2.𝛼 2 = 𝐾𝑎 𝐶. ( 𝑎 )
𝐶

𝐾𝑎 2
[H+]2 =
𝛼2

𝐾𝑎
And [H+] =
𝛼

NOTE
1
C=
v

Example
1. A 0.01M solution of chloromethanoic acid is 18% ionized. Calculate the PH of the
solution and Ka of the acid
Solution
𝛼 = 18%
= 0.18
C = 0.01M
𝐾𝑎
𝛼=√
𝐶
𝛼 2 𝐶 = 𝐾𝑎 , 𝐾𝑎 = 𝛼 2 𝐶
= 0.182 × 0.01
= 3.24 × 10-4 moldm-3
[H+] = √𝐾𝑎 𝐶
= √3.24 × 10−4 × 0.01
= 1.8 × 10-3
And PH = - log (1.8 × 10-3)
= 2.745

127
 2. The PH of a 0.001M solution of an acid is 3.59
Calculate
i) Dissociation constant
ii) Degree of dissociation

Solution
i) PH= - log [H+]
3.59 = - log [H+]
And [H+] = 10-3.59
= 2.57 × 10–4
But [H+] = √𝐾𝑎 𝐶

(2.57 × 10-4)2 = Ka × 0.001

Ka = 6.61 × 10-5 mol l-1

ii)  = Ka
C
= 6.61 × 10-5
0.001
= 0.257
= 2.57 ×10-1

Self check
1. Calculate the PH of 0.02M H2SO4
(Ans. 1.3979)
2. Calculate the molarity of a solution of H2SO4whose PH is 4.35
(Ans. 2.23 × 10-5)
3. The PH of 0.001M methanoic acid is 3.63 calculate
a) Dissociation constant Ka of the acid
b) The PKa of the acid
c) The degree of dissociation of the acid
(Ans. a = 5.48 × 10-5mol l-1 b = 4.26 𝜶 = 0.234)

THE PH OF ALKALIS
Consider
NaOH(aq) Na+(aq) + ŌH(aq)

128
 [OH] = [NaOH]

From Kw = [H+] [ŌH]

[H+] = Kw
[ŌH]
PH = - log[H+]

= - log Kw
ŌH
PH = - logKw + log[OH]
PH = log[ŌH] - logKw
Or
PH = - logKw – (- log[ŌH]
= - logKw – P(-OH)
PH = 14 – POH

As in the case of acids, [ŌH] can be got from [ŌH] = KbC where Kb is the base dissociation
constant of a weak base.

Example
1. Calculate the PH of a solution of 0.0M NaOH solution

Solution
[ŌH] = 0.02
PH = 14 – POH
= 14 + log(0.02)
= 12.301
2. The Ksp of Mg(OH)2 is 8.8 × 10-12 mol3l-3, what is the PH of a saturated solution at
equilibrium
(Kw = 1 ×10-14)
Solution
Mg(OH)2(s) Mg2+(aq) + 2ŌH(aq)

Let 𝑥 be [Mg2+]
Then [ŌH] = 2𝑥
Ksp = [Mg2+] [ŌH]2
8.8 ×10-12 = 𝑥. 4𝑥 2
4𝑥 3 = 8.8 ×10-12
4 4
3
𝑥 = 2.2 x 10-12

129
 3
𝑥 = √ 2.2 × 10−12
= 1.3 × 10-4mol l-1

Therefore [ŌH] = 2 × 1.3 ×10-4

= 2.6 ×10-4mol l-1.
PH = - logKw – POH
PH = 14 – POH
PH = 14 – (-log 2.6 × 10-4)
= 10.4

Self Check
1. Calculate the concentration in mol l-1 of Mg2+ in a solution of Mg(OH)2 whose PH is
10.61
(Ans. 2.037 × 10-4 mol l-1)
2. A solution of 0.4M XOH of 1.4 × 10-5
a) Calculate the dissociation constant of the weak base XOH
b) What is the [H+] of 0.4M XOH
c) Calculate the PH of the solution
d) What is the concentration of ŌH in a solution of 0.1M XOH (Kw =1 ×10-14)
(Ans. a) Kb= 4.9 × 10-10mol l-1 b). 7.143 × 10-10mol l-1) c). PH= 9.146 d). 7.0 ×10-6mol l-1)
3. A 0.01M solution of phenylamine is 8% ionized calculate
a) The base dissociation constant
b) PH of solution
(Ans. a) Kb= 6.4 × 10-5 mol dm-3 b). PH= 10.9)

Example
The molar conductivity of 0.05M solution of benzoic acid at 250C is 9.46 ×10-4-[Link]
the molar conductivities at zero concentration of H+ and C6H3COŌ are 2.8 × 10−2 and 6 ×
10−2 Ὠ-1cm2mol-1 respectively.
Calculate a). The degree of dissociation of the acid
b). The dissociation constant of the acid
c). PH of solution
Solution
a) Using 𝛼 = 


 C6C5OOH = H+ + C6H5COŌ

= 2.8 × 10 + 6 ×10-2
-2

= 8.8 ×10-2cm2mol-1

130
And 𝛼 = 9.46 × 10-4
8.8 ×10-2
= 1.075 × 10-2
𝐾𝑎⁄
b) 𝛼=√ 2
𝑐 and 𝛼 𝐶 = Ka
 (1.075 × 10-2)2 × 0.05 = Ka
Ka = 5.778 × 10-6 mol l-1

c) PH= - log [H+]

= - log (5.375 ×10-4)
= 3.27
NOTE
1. PK values are defined as
PKa= - logKa
PKb= - logKb
The higher the value of Ka or Kb the stronger is the acid or base.
2. For conjugate acid – base pairs.
PKa + PKb= PKw example,
a) Given that PKa of NH4+ at 250C is 9.25, calculate the PH of an aqueous solution of 0.1M NH3
solution
Solution
From PKa+ PKb = PKw
PKb = PKw – PKa
= 14 – 9.25
= 4.75
And PKb = - logKb
4.75 = - logKb
Kb= 1.778 × 10-5 mol l-1
Then [ŌH] = √𝐾𝑏 𝑐

= √1.778 × 10−5 × 0.1

= 1.33 ×10-3 mol l-1
Thus PH= 14 – POH
= 14 – (-log 1.33 ×10-3)
=11.12

Self check
1. Calculate the PH of a 0.003M ethanoic acid whose PKs is 9.24 ( Kw =10-14)
(Ans. PH = 5.88)

131
 SALT HYDROLYSIS
Hydrolysis is a reaction between H2O and another species to form an associated species plus H+
or ŌH.
Salts of strong acids and weak bases and those of strong bases and weak acids undergo
hydrolysis in aqueous solutions.
Consider the equilibrium of water (H2O)
H2O(l) H+(aq) + ŌH(aq)
If any species is added which associates with either ŌH or H+ ions. The H2O equilibrium shifts
to the right to produce excess H+ or ŌH ions.

If NaCl is added to H2O, there is no hydrolysis; the Na+ and Cl- do not affect the H2O
equilibrium because there is no possibility of forming associated species. The Na+ and ŌH do not
associate because NaOH is a strong electrolyte and so is HCl acid. But if sodium ethanoate
(CH3COŌNa+) is added to H2O hydrolysis occurs because CH3COŌ ions associate with H+ ions
to form ethanoic acid (CH3COOH) species
H2O(l) H+(aq) + ŌH(aq) (1)
+
CH3COO(aq) + H CH3COOH(aq) (2)
+
The CH3COŌ in (2) combine with H from (1) and this disturbs the equilibrium of H2O. To
restore Kw more H2O ionizes. This puts ŌH concentration in excess and solution would have a
PH greater than 7. Thus an aqueous solution of a salt from a weak acid and strong base is
alkaline. The net effect is the sum of the two equations above.
CH3COŌ(aq) + H2O(l) CH3COOH(aq) + ŌH(aq)
A salt from a strong acid and weak base forms an acidic solution in H2O example hydrolysis of
phenyl ammonium chloride.
CH5NH3Cl C6H5N+H3 + Cl-
In solution
C6H5+NH3 + H2O C6H5NH3OH + H+
Since phenyl ammonium hydroxide is a weak base the solution is acidic due to excess H+
formed.
Consider the following hydrolysis
A- + H2O HA + ŌH
The hydrolysis constant is give by;
Kh = [HA] [ŌH]
[A-]
In solution the following equilibrium exist
H2O H+ + ŌH
HA H+ +A-
Kw = [ŌH] [H+]

132
 Ka= [H+] [A-]
[HA]
From above, eliminating [H+]
Kw = [ŌH] [HA] = Kh
Ka [A-]

Therefore, Kh = Kw
Ka

Example
1. Calculate the PH of a solution of CH3COONa made by dissolving 8.4g in 1dm3 of H2O if
the hydrolysis Constant is 5.5 × 10-10 moldm-3
Solution
CH3COONa(s) CH3COŌ(aq) + Na+(aq)
CH3COŌ(aq) + H2O(l) CH3COOH + ŌH
Kh = [CH3COOH] [ŌH]
[CH3COŌ]
Kh = [ŌH]2
[CH3COŌ]

And [CH3COŌ] = C = [salt]

Kh = [ŌH]2
C
[OH] = √𝐶𝐾ℎ
8.4
=√ × 5.5 × 10−10
82

= 7.51 × 10-6moldm-3

PH= 14 – (- log[ŌH])
= 14 + log[7.51 × 10-6]
= 8.88
2. Calculate the PH of 0.1m CH3COONa if it’s Kh is 5.6 × 10-10
Solution
CH3COONa(s) CH3COŌ(aq) + Na+(aq)
Kh = 5.6 x 10-10
C = 0.1
CH3COŌNa(s) CH3COŌ(aq) + Na+(aq)
CH3COŌ(aq) + H2O CH3COOH(aq) + ŌH(aq)
Kh = [CH3COOH] [ŌH]

133
 [CH3COŌ]
= [CH3COOH] [ŌH]
C
Kh = [ŌH]2

C
[ŌH] = √ 𝐶𝐾ℎ

= √0.1 × 5.6 × 10−10

= 7.48 × 10-6mol l-1

And PH =14 – (- log[ŌH] )

=14 – (- log 7.48 × 10-6)
= 8.87
3. (a)(i). Ammonia undergoes the following reaction in H2O
NH3(g) + H2O(l) NH4+(aq) + ŌH(aq)
Write the expression for base dissociation constant Kb for NH3
ii). Water ionizes according to the equation
H2O + H2O(l) H3O+(aq) + ŌH(aq)
Write an expression for ionization constant Kw of H2O
iv). The hydrolysis of NH4Cl is given by the equation
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
Express the hydrolysis constant Kh for NH4Cl in terms of Kb and Kw
b) Calculate
i). The hydrolysis constant Kh for ammonium chloride given Kw= 10-14 and Kb = 1.8 × 10-5
ii). The [H+] of a 0.01M NH4Cl solution
iii). The PH of the solution

Solution
a(i). Kb= [NH4+] [ŌH] assume H2O is in excess and its concentration remain constant
[NH3]
ii). Kw = [H3O+] [ŌH]
Kh = [NH3] [H3O+]
[NH4+]
(ii)  (i)
Kw = [H3O+] [ŌH] [NH3]
Kb [NH4+] [ŌH]
= [H3O+] [NH3]
[NH4+]
= Kh
10−4
Then Kh =
1.8 ×10−5

134
 Fe3+ + 3C6H5NH2+(aq) 3H2O(l) Fe(OH)3(s) + 3C6H5NH3+(aq)
i) Write an expression for the equilibrium constant for the reaction.
ii) Express the equilibrium constant in terms of Ksp and Kb
iii) Calculate the value of the equilibrium constant
iv) What does the value of this constant signify
𝟑
(Ans. Kc = 𝑲𝒃 ⁄𝑲 , K= 7.95 x 109 l mol-1, (By value of Kc means that the equilibrium lies
𝒔𝒑
very much to the right)

BUFFER SOLUTIONS

A buffer solution is a mixture of a weak acid and its salt formed when it reacts with a strong base
or a weak base and its salt formed when it reacts with a strong acid. Such a mixture maintains a
constant PH when a small amount of alkali or acid is added. There are two types of buffers i.e.
a) Acidic buffers.
b) Basic buffers.

ACIDIC BUFFER
An acidic buffer consists of a weak acid and its salt from a strong base example
CH3COOH / CH3COONa, H2CO3 /NaHCO3

Action of an acidic buffer

Consider a mixture of CH3COOH and CH3COONa.
CH3CooH is slightly dissociated and CH3COONa is highly dissociated.
CH3COOH(aq) CH3COŌ(aq) + H+(aq) (1)
+
CH3COONa(aq) CH3COŌ(aq)+ Na (aq) (2)

This solution will contain excess CH3COŌ and a larger reservoir of an ionized CH3COOH
molecules and small amount of H+ ions .If a small amount of H+ ions added combines with
CH3COŌ to form un ionized CH3COOH . Therefore the PH will remain unchanged. Addition of
ŌH from NaOH, KOH, the ŌH will react with H+ ions from (1) to form H2O and the PH remains
constant. Thus addition of ŌH or H+ does not change PH.

BASIC BUFFERS
A basic buffer consists of a weak base present together with its salt from a strong acid example
NH4OH/NH4Cl

Action of a basic buffer

In solution the base is slightly ionized while the salt is fully ionized
NH4OH NH4+(aq) + ŌH(aq) (1)
+
NH4Cl(aq) NH4 (aq) + Cl(aq) (2)

136
The solution has excess NH4+, large reservoir of NH4OH and small amount of ŌH.
Additions of H+ ions react with ŌH from (1) to form H2O and the PH remains constant.
Addition of ŌH react with NH4+ (excess) from (2) to form unionized NH4OH and the PH
remains constant.

PH OF BUFFER SOLUTIONS
The PH of a buffer solution can be calculated from the dissociation constant of the weak acid or
base and the concentration of the salt present in the mixture.
Acidic Buffers
CH3COOH(aq) CH3COŌ(aq) + H+(aq)
Ka = [CH]3COŌ] [H+]
[CH3COOH]
+
[H ] = Ka [CH3COOH]
[CH3COŌ]

The acid is slightly dissociated and its concentration is regarded as being constant. The salt is
highly dissociated and the concentration of CH3COӦ is regarded as derived entirely from
CH3COONa. Therefore,
[H+] = Ka [acid]
[Salt]

PH= - log[H+]
= - log Ka [acid]
[Salt]

= - log Ka + log [acid]

[Salt]
= Pka + log [salt]
[acid]
If [salt] = [acid]
Then PH = PKa

Basic Buffer
NH4OH/NH4Cl
NH4OH(aq) NH4+(aq) + ŌH(aq)
NH4Cl(aq) NH4+(aq)+ Cl-(aq)

Kb = [NH4+] [ŌH]
[NH4OH]
[ŌH] = Kb [NH4OH]
[NH4+]

137
Since NH4Cl is fully ionized
[NH4+] = [salt] and NH4OH is slightly dissociated so that
[NH4OH] = base

Therefore [ŌH] = Kb [base]

[Salt]
And PH = - log Kb [base]
[Salt]

= - logKb + log [salt]

[Base]
Ka
= P + log [salt]
[Acid]
NOTE:
PH = 14 – POH

Examples;
1. Calculate the PH of a buffer which consists of 4.1g of CH3COONa per litre of solution. And
0.01M CH3COOH whose Ka = 1.7 × 10-5moldm-3

Solution
RFM of CH3COONa = 82
[Acid] = 0.01M
[Salt] = 4.1
82
= 0.05m

CH3COOH(aq) CH3COŌ(aq) + H+(aq)

Ka = [CH3COŌ] [H+]
[CH3COONa]

[H+] = Ka [acid]
[Salt]

= 1.7 × 10-5 × 0.01

0.05
= 3.4 × 10-6 moldm-3

PH = - log [H+]
= - log 3.4 × 10-6

138
 = 5.469
2. a). 3.2g of CH3COONa are added to litre of a 0.01M solution of CH3COOH. Calculate
the PH of the mixture
b) If 1cm3 of 1M HCl is added to one litre of the above mixture, calculate the new PH.
c). Calculate the change in PH when 1cm3 of 1M NaOH is added to one litre of the above
mixture in (a)
(Ka= 1.84 ×10-5), Na=23, O=16, C =12, H=1)

Solution
R.F.M of CH3COONa = 82
[Salt] = 3.28⁄82
= 0.04M
[Acid] = 0.01M
[H+] = Ka [acid]
[Salt]
= 1.84 × 10-5 × 0.01
0.04
[H ] = 4.6 ×10-6 moldm-3
+

PH2 = - log (4.6 × 10-6)

= 5.34

b). Addition of 1cm3 of 1M HCl to one litre of H2O would give a solution of [H+] = 0.001mol l-1
(approximately)
0.01 + 0.001
CH3COOH CH3COŌ + H+
CH3COONa CH3COŌ + Na+
0.04 – 0.001
The combination of H+ and CH3COŌ of the salt increases the concentration of CH3COOH
molecules from 0.01 to 0.011M and this reduces the concentration of CH3COŌ from 0.04 to
0.039M
Therefore,
New concentration of acid = 0.011M PH = - log[H+]
[Salt] = 0.039M = - log (5.19 × 10-6)
[H+] = Ka [acid] = 5.28
[Salt]
= 1.84 × 10-8 × 0.011
0.039
= 5.19 × 10-6mol l-1

139
c) When NaOH is added to the solution it reacts with ethanoic acid, this causes concentration of
ethanoic to fall while concentration of salt increases.
1cm3 of 1M NaOH = 1⁄1000 moles (approximate)
= 0.001
New [acid] = 0.01 – 0.001
= 0.009M
[Salt] = 0.04 + 0.001
= 0.041

[H+] = Ka [acid]
[Salt]
= 1.84 × 10-5 × 0.009
0.041
= 4.04 × 10-6 mol l-1
Then PH = - log 4.04 × 10-6
= 5.39
Change in PH = 5.39 – 5.34
= 0.05

3. 20cm3 of 0.1M NaOH solution was added to 100cm3 of 0.1M solution of CH3COOH,
calculate the PH their resulting solution (Ka = 1.7 ×10-5)

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

Moles of NaOH in 20cm3 = 20 × 0.1

1000
= 0.002 moles
Moles of acid = 100 × 0.1
1000
= 0.01 moles

Moles of acid left = 0.01 – 0.002

= 0.008 moles
Total volume of solution = 20 + 100
= 120cm3

120cm3 of solution contain 0.002 moles of salt

1000cm3 of solution contain 0.002 × 1000
120
= 0.0167M
Then [salt] = 0.0167M

140
 Similarly, [acid] = 0.008 × 1000
120
= 0.067M
[H+] = Ka [acid]
[salt]
= 1.7 × 10-5 × 0.067
0.0167
= 6.82 ×10-5mol l-1
PH = - log 6.82 x 10-5
= 417

Self Check
1. 0.03 moles of NH4Cl are added to one litre of 0.01M NH3 solution. Calculate.
a) Concentration of ŌH in solution
b) PH of the solution (Kb = 2 × 10-5, Kw =10-14)
(Ans. a = 6.67 x 10-6 mol l-1 b = 8.82)

2. Calculate the PH of a solution which was made by adding 30cm3 of 0.1M HCl to 80cm3
of 0.1M NH3 solution (Kb= 1.8 x 10-5 moldm-3)
(Ans. 9.477)

3. Calculate the mass of CH3COONa that should be added to one litre of 0.1M CH3COOH
in order to give a solution whose PH is 4. State any assumptions made. (Ka = 1.8 × 10-5)
(Ans. 1.476gl-1)

Assumptions
 There is no volume change of the solution on addition of CH4COONa.
 The concentration of acid does not change because the added CH3Coō should increase
the concentration of acid by shifting equilibrium to the left.
CH3COOH CH3COŌ + H+

Applications of buffer solutions

 In medicine and agriculture to prepare standard solutions since PH of living cells must be
maintained
 A buffer solution is used by the body in maintaining the PH of its fluids.
 In fermentation process. Most fermentation processes must be carefully buffered because
any change in PH would cause death of the fermenting organisms.

141
 THEORY OF INDICATORS

Indicators are substances which vary in colour according to [H+] of the solution which they are
added. They are either weak acids or weak bases.
Most indicators used in acid alkali titrations are weak acids and their degree of dissociation is
greatly affected by the PH of the solution.
Different indicators change colour over different ranges of [H+] example

Indicator PH range Acid Alkali

Methyl orange 3.0 – 5.0 Red yellow
Phenolphthalein 8.3 - 10.0 colourless Pink
Litmus 5.0 - 8.0 Red Blue

Action of an indicator
1. Methyl Orange (CH3)2N o N= N o SO3H that is, HA
When dissolved in water H2O an equation is set up. That is,
HA A- + H+
Red yellow
The red colour is due to undissociated HA and the yellow colour is due to dissociated A- ions.
Addition of ŌH ions increases the number of A- ions enough to show their yellow colour.

Addition of an acid provides H+ ions which reduce A- ions and form more HA which is red

2. Phenolphthalein indicator (PhH)

In solution it ionizes as
HPh H+ + Ph
Colourless pink

Addition of ŌH removes H+ to form H2O. This decreases [H+] and hence to restore the
equilibrium more HPh dissociates and increases [Ph-] hence the indicator shows the colour of the
dissociated ion which is pink

END POINT
At the end point the number of HPh molecules and Ph- ions present are equal because the two
colours of the indicator will be shown t an equal extent.
This occurs at different Ph of each indicator.
If Ka is the dissociation constant of the indicator then
Ka = [H+] [Ph-]
[HPh]
+
[H ] Ka = [HPh]
[Ph-]

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Since at the end point [HPh] = [Ph-] then,
[H+] = Ka
And PH = - log [H+]
= - log Ka

For the case of phenol indicator

Ka = 7 × 10-10moll-1 and the corresponding PH is 9.1
For methyl orange
Ka = 2 ×10-4 moll-1 and the corresponding PH is 3.7

PH Change during titration

During titration the PH of the solution changes as acid or base is added. The change depends on
the strength of the acid or alkali used.
It’s important to use an indicator which changes colour around the range in which a marked PH
change during the reaction occurs.

Example
Titration Marked PH change indicator
Strong/strong base 4 -10 Most indicator
Weak acid/strong base 7.5 - 10.5 Phenolphthalein
Weak acid /weak base No marked range No indicator

TITRATION CURVES
Titration of a strong acid against a strong alkali

PH 14 D

7 End point

1
Litre Volume
Volume of alkali
Explanation
PH at A is due to strong acid which is completely ionized. A gradual rise in PH a long AB is due
to removal of H+ (hydrogen ions) from solution. At the end point the PH sharply rises and it is at
7 because no hydrolysis of the salt. The rise PH along CD is due to excess alkali after the end-
point.

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 NB
Methyl orange, litmus paper and phenolphthalein indicators can be used under this titration
because they have a range of PH between 3.5 and 9.5
Titration of weak acid against strong base

14 D

7 End
point
B

2
A
TH volume

Volume of alkali

At A the PH is due to weak acid, but gradually increases along AB due to removal of
H+(hydrogen ions) from the solution. At the end point it rapidly rises and the resultant solution
has a PH greater than 7 due to hydrolysis of the salt and along the CD, the PH rises due to excess
alkali.
NB Phenolphthalein is the only suitable indicator because it has PH range between 7.5 and 10.5

Titration of weak base against strong acid

12
PH

Volume of alkali

At the beginning the PH is low because the acid is completely ionized. There is a gradual
increase in PH as the base is added because neutralization, takes place forming salt and water
The remaining acid is diluted by the increased volume of water so concentration of hydrogen
ions decreases and PH increases. Towards the end-point the remaining acid is neutralized and is
highly diluted .there is a rapid increase in PH as the acid is completely neutralized. The PH at the

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equivalent point is below seven due to hydrolysis of the salt. There is a gradual increase in PH as
the base is added because there is no acid for the weak base to react with. But because the base is
weak and exists mainly as molecule, PH rises only towards 10 and not 14.
NB
Phenolphthalein and thymolblue are unsuitable indicators
Titration of strong acid with a weak base
A
PH B

Volume of acid

PH at A is due to the weak base. But gradually decreases along AB as the acid is added because
of increase in concentration I hydrogen ions and decrease in concentration of hydroxyl ions. At
the end-point there is a rapid decrease in PH along BC
The PH at the end-point is below due to the hydrolysis of the salt formed. The rapid decrease in
PH along CD is due to excess acid added.

Self check
1. a) Draw diagrams to show the change in PH when a 0.1M sodium hydroxide solution is
added in portions to
i) 20cm3 of a 0.1M hydrochloric acid.
ii) 20cm3 of a 0.1M ethanoic acid explain the shapes of the curves.
a. Sketch a graph to show the variation of PH during the titration of hydrochloric acid
with ammonia solution and explain the shape of the graph.
2. Sodium hydroxide solution was added to 25cm3 of 0.1M ethanoic acid and the PH of the
solution was measured at intervals the results are given in the table below.
Volume of NaOH/Cm3 0 4 8 12 16 20 22 22.5 23 24 28
PH of mixture 2.8 3.5 4 4.5 5.1 5.8 7 9 10.5 11.4 12.3

i) Plot a graph of PH against volume of sodium hydroxide

ii) Explain the shape of the curve.
iii) Determine the PH at the end point
iv) Calculate the morality of sodium hydroxide solution
b). Determine the dissociation constant ka of ethanoic acid
c). Describe how sodium hydroxide can be prepared on a large scale
(Ans. a ) iii) 9 =0.2 iv) 0.11M b). Ka= 2.5 x 10-5)

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