SKA 1023

SKILLS AND CONCEPTS IN ANALYTICAL

CHEMISTRY
CHAPTER 5
Acid-Base Equilibrium
ACID-BASE EQUILIBRIUM

CONTENTS

5.1 Introduction
5.2 Acid-base theories
5.2.1 Arrhenius theory – H+ and OH-
5.2.2 Bronsted-Lowry theory – taking and
giving protons
5.2.3 Lewis theory – taking and giving
electrons
5.3 Ionization of acid-base in water
5.4 Water dissociation
5.5 Scales and pH calculations
2
CONTENTS

5.6 Strong acid and strong base

5.7 Weak acid and weak base
5.8 Salts of weak acid and weak base
5.9 Buffer solutions
5.9.1 Buffer solution of a weak acid
5.10 Introduction to acid-base titration
5.11 Standard solution
5.12 Titration classifications
5.13 Acid–Base titration
5.13.1 Strong acid vs strong base
5.13.2 Weak acid vs strong base
5.14 Acid-Base Indicators
3
5.1 INTRODUCTION

The acidity or basicity of a solution is frequently an

important factor in chemical reactions
The use of buffers of a given pH to maintain the solution
pH at a desired level is very important
In addition, fundamental acid-base equilibria are
important in understanding acid-base titrations and the
effects of the acids on chemical species and reactions, for
example, the effects of complexometric or precipitation

4
ACID-BASE THEORIES
Several acid-base theories have been proposed to explain
or classify acidic and basic properties of substances

ARRHENIUS THEORY – H+ AND OH-

An acid – any substance that ionized partially or
completely dissociates in water to give hydrogen ions
(which associate with the solvent to give the hydronium
ions, H3O+)
HCl + H2O  H3O+ + Cl-
A base – ionizes in water to give hydroxide ions
Weak (partially ionized) bases generally ionized as follows
NH3 + H2O  NH4+ + OH-
5
ARRHENIUS THEORY – H+ AND OH-

Strong base such as metal hydroxide (e.g. : NaOH)

dissociate as
NaOH  Na+ + OH-
This theory is obviously restricted to water as the solvent

6
BRØNSTED-LOWRY THEORY –
TAKING AND GIVING PROTONS

An acid – any substance that can donate a proton (H+)

A base – any substance that can accept a proton
It is apparent from the above definition that a substance
cannot act as an acid unless a base is present to accept
the protons

Acid1 H+ + Base1
Base2 + H+ Acid2

# Acid1 and Base1 are conjugate pairs, and so are

Base2 and Acid2

7
BRØNSTED-LOWRY THEORY –
TAKING AND GIVING PROTONS

CH3COOH + H2O H3O+ + CH3COO-

acid1 base2 acid2 base1

When acetic acid is dissolved in water, dissociation take

place since the solvent (water) acts as a base or a proton
acceptor
CH3COO- ion is a base conjugate for CH3COOH

8
BRØNSTED-LOWRY THEORY –
TAKING AND GIVING PROTONS

NH3 + H2O NH4+ + OH-

base1 acid2 acid1 base2

When ammonia is dissolved in water, the solvent (water)

acts as an acid or a proton donor
NH4+ ion is a conjugate acid for base NH3

HCl + NH3  Cl- + NH4+

acid base

9
LEWIS THEORY – TAKING AND
GIVING ELECTRONS
An acid – a substance that can accept an electron pair
A base – a substance that can donate an electron pair
H+ + :NH3  H:NH3+
R
AlCl3 + :O  Cl3Al:OR2
R
H
O: + H+  H2O:H+
H
H+ + :OH-  H:OH
The Lewis theory assumes a donation (sharing) of
electrons from a base to an acid
10
IONIZATION OF ACID-BASE IN
WATER

When acid or base is dissolved in water, it will dissociate

or ionize
The amount of dissociation depends on the strength of
the acid or base
The reaction between acid and water is known as
dissociation reaction or ionization of acid
Strong acid is an acid that ionizes completely, example
HCl
Weak acid is an acid that ionizes partially, example
CH3COOH

11
IONIZATION OF ACID-BASE IN
WATER

The dissociation reactions are as follows :

HCl + H2O  H3O+ + Cl-

CH3COOH + H2O H3O+ + CH3COO-

The arrow sign  indicates a complete dissociation

whereas this arrow sign indicates a partial
dissociation

12
IONIZATION OF ACID-BASE IN
WATER

The strength of a base depends on the total amount of

the hydroxide concentration, OH-
A strong base is a substance that dissociates completely
to give OH-, example NaOH
A weak base is a base that dissociates partially, example
acetate ion, CH3COO-

NaOH  Na+ + OH-

CH3COO- + H2O CH3COOH + OH-

13
WATER DISSOCIATION

Water is an amphiprotic solvent that is having acidic and

basic properties
Water undergoes autoprotolysis as follows :

H2O + H 2O H3O+ + OH-

or

2H2O H3O+ + OH-

H2O H+ + OH-
Kw = [H+] [OH-] = 1.0 X 10-14 M2
[H+] = [OH-] = 1.0 X 10-7 M
14
 EXERCISES

(1) A 1.0 X 10-3 M solution of hydrochloric acid is prepared. What is

the hydroxyl ion concentration ?

Since hydrochloric acid is a strong electrolyte and is completely

ionized, the H+ concentration is 1.0 X 10-3 M. Thus,

(1.0 x 10-3) [OH-] = 1.0 X 10-14 M

[OH-] = 1.0 X 10-11 M

15
SCALES AND pH CALCULATIONS
When discussing chemical equilibrium, we will encounter a very low
concentrations
From the water dissociation constant, Kw = 1.0 X 10-14 M2, we can then
calculate a range of a very low hydrogen ion and hydroxide ion
concentrations of 10-14 M to a higher concentration, such as 0.1 M
The pH of a solution was defined as

pH = - log [H+]

A similar definition is made for the [OH-]

pOH = - log [OH-]

pKa = - log Ka

Kw = [H+] [OH-]

- log Kw = - log [H+] [OH-] = - log [H+] – log [OH-]

16
SCALES AND pH CALCULATIONS
The equation in logarithm form for a more direct
calculation of pH or pOH is

pKw = pH + pOH

At 25oC, Kw = 1.0 X 10-14 M2, then

14.00 = pH + pOH

[H+] = [OH-] = 1.0 X 10-7 M

When
[H+] = [OH-], then a solution is said to be neutral
[H+] > [OH-], then the solution is acidic
[H+] < [OH-], the solution is alkaline or basic
17
 EXERCISES

(1) Calculate the pH of a 2.0 X 10-3 M solution of HCl.

HCl is completely ionized, so

-
104

[H+] = 2.0 X 10-3 M

pH = - log (2.0 X 10-3)
= 2.70

18
 EXERCISES

(2) In NaOH solution [OH-] is 5.0 X 10-2 M. Calculate the pH of the

solution.

[OH-] = 5.0 X 10-2 M

pOH = - log (5.0 x 10-2)
= 1.30

pH + 1.30 = 14.00
pH = 12.70

19
 EXERCISES

(3) Calculate the pH of a solution prepared by mixing 2.0 mL of a

strong acid solution of pH 3.00 and 3.0 mL of a strong base of pH
10.00.

[H+] of acid solution = 1.0 x 10-3 M antilog : shift 109

mmol H+ = (1.0 X 10-3 M) X (2.0 mL) -
(x)
= 2.0 X 10-3 mmol
pOH of a base solution = 14.00 - 10.00 = 4.00
[OH-] = 1.0 X 10-4 M * 3 0 mL 3 0 X 10 mmol
. = .

There is an excess of acid,

mmol H+ = 0.0020 - 0.0003 = 0.0017 mmol
[H+] = 0.0017 mmol / 5.0 mL = 3.4 X 10-4 M
pH = - log (3.4 X 10-4) = 3.47
20
 EXERCISES

(4) The pH of a solution is 9.67. Calculate the hydrogen ion

concentration in the solution.

- log [H+] = 9.67

[H+] = antilog 9.67
= 2.1 X 10-10 M

21
 EXERCISES

(5) Calculate (a) pKw for water ionization constant, and (b) pH and pOH
values for 1.5 X 10-3 M hydrogen ion solution

(a) pKw = - log [Kw]

= - log (1.0 X 10-14)
= 14.00

(b) [H+] = 1.5 X 10-3 M

pH = - log (1.5 X 10-3)
= 2.82

pOH = 14.00 - 2.82

= 11.18

22
 25
10
.

EXERCISES PH

25
(6) Calculate [H+] for a solution of pH 10.25

pH = - log [H+]
= 10.25
% 20 "m
 [H+] = antilog 10.25
or = 10-10.25
= 5.6 X 10-11 M

23
STRONG ACID AND STRONG BASE

Strong acid and strong base will dissociate completely in

water
If the concentrations of acids and bases are less than 10-
7 M, then the H+ contribution from strong acid or OH- from

strong base is neglected as compared to the H+ and OH-

contribution from water
Hence the pH calculation is based on H+ or OH- from water
only
If the acid or base concentration is around 10-7 M, then
the H+ or OH- contribution from water has to be taken into
account

24
STRONG ACID AND STRONG BASE
de sociate
compeletly .

If the concentrations of strong acid and base are greater

than 10-7 M, then the pH calculation is based on the
concentrations of strong acid and base
The equilibrium constants for strong acids and bases are
not listed in the table of equilibrium constants because
the values are too large and may be infinity
Example of strong acids are HClO4, HCl and HNO3
Examples of strong bases are NaOH, Ca(OH)2 and KOH

25
EXERCISES

~
(1) Calculate the pH of 1.0 X 10-2 M NaOH solution

Kw = [H+] [OH-] Kw :
CH
+
]20w]
[H+] = Kw
[OH-]
= 1.0 X 10-14
ht
1.0 X 10-2
:

ot
= 1.0 X 10-12 M
:
1x10-18.j 12)
-

pH = - log (1.0 X 10-12)

= 12.00
PH
=
-10
26
 EXERCISES

(2) Calculate the pH and the pOH of 1.5 X 10 -7 M HCl solution

Since hydrochloric acid is a strong electrolyte and is completely

ionized, the H+ concentration is 1.5 X 10-7 M. Thus,

pH = - log [H+]
= - log (1.5 X 10-7)
= 6.82

pOH = 14.00 - pH
= 14.00 - 6.82
= 7.18

27
WEAK ACID AND WEAK BASE

Weak acids and weak bases will ionize partially

For weak acids, ionization constant, dissociation constant
or acidity constant (Ka) is used to calculate the total H+
that has ionized
The basicity constant (Kb) is used to calculate the total
amount of OH- ionized
Example acetic acid, CH3COOH with a concentration of C

28
 C 00
initial an
N
cani C -

WEAK ACID AND WEAK BASE

CH3COOH H+ + CH3COO-

Initial (M) C 0 0
Equilibrium (M) C–x x x
h
Ka = [H+] [CH3COO-] = 1.75 X 10-5
[CH3COOH]
:
(x)(x) = 1.75 X 10-5 t
1
=
C–x

29
WEAK ACID AND WEAK BASE

x or H+ concentration can be determined by solving the

quadratic equation or the expression can be classified by
neglecting x at the denominator if C > 100 Ka or Ka
< 0.01 C
If x at the denominator is neglected, the general formula
to determine [H+] for weak acid (HA) with a concentration
of CHA :
[H+] =  KaCHA

30
WEAK ACID AND WEAK BASE

For weak base, example NH3 with basicity constant, Kb will

undergo the following reaction in water
NH3 + H2O NH4+ + OH-

The same method can be applied to determine [OH-] for

weak base
The general formula to determine [OH-] for a weak base
(B) with a concentration of CB :
[OH-] =  KbCB

31
 O
:A
100x10200
:
initial
ka
xit)
un2
EXERCISES
-

00
(1
+

u
=

S
(1) Calculate the pH of 1.00 X 10-2 M acetic acid solution. Given Ka
acetic acid is 1.75 X 10-5.

1
.
75
x10-5
CH3COOH H+ + CH3COO-

Iwe Initial (M)

Equilibrium (M)
1.00 X 10-2
(1.00 X 10-2) - x
0
x
0
x

Ka = [H+] [CH3COO-] = 1.75 X 10-5

[CH3COOH]

(x)(x) = 1.75 X 10-5

(1.00 x 10-2) – x
32
EXERCISES

x at the denominator can be neglected since C > 100 Ka

(x)(x) = 1.75 X 10-5

1.00 x 10-2

x = 4.18 X 10-4 M = [H+]

pH = - log [H+]
= - log (4.18 X 10-4)
= 3.38

33
SALTS OF WEAK ACID AND WEAK
BASE

Salts of weak acids (example NaOAc, CH3COONa) are

strong electrolytes and ionize completely in water
The anion of a weak acid salt is a BrØnsted base, which
can accept a proton from water to form hydroxide ion and
acid
The acid does not dissociate or the anion of the weak acid
salt can undergo hydrolysis
Example, sodium acetate salt (NaOAc) is from acetic acid

34
SALTS OF WEAK ACID AND WEAK
BASE

NaOAc  Na+ + OAc-

OAc- + H2O HOAc + OH-

The equilibrium for the salt of weak acid is given below

KH = Kb = [HOAc] [OH-]
[OAc-]
KH = hydrolysis constant
Kb = basicity constant

35
SALTS OF WEAK ACID AND WEAK
BASE

KH = Kb = [HOAc] [OH-] X [H+]

[OAc-] [H+]
KH = K b = K w
Ka
Kw = KaKb

Therefore, the product of Ka for any weak acid and Kb for

its conjugate base is equal to Kw

36
SALTS OF WEAK ACID AND WEAK
BASE

Salts of weak base is a BrØnsted acid and can ionize or

hydrolyze completely in water
Example, NH4Cl salt from a weak base, NH3
NH4Cl  NH4+ + Cl-
NH4+ + H2O NH3 + H3O+

NH3 does not dissociate and does not contribute for the
pH

37
SALTS OF WEAK ACID AND WEAK
BASE
kh : Ka .
KH = Ka = [NH3] [H3O+] 6b
=
kn
[NH4+] ko :

KH = Ka = [NH3] [H3O+] X [OH-]

[NH4+] [OH-]
KH = Ka = Kw
Kb
Kw = KaKb

38
 EXERCISES

(1) Calculate the pH of 1.0 X 10-2 M NaOAc solution. Ka for HOAc is

1.75 X 10-5.

OAc- + H 2O HOAc + OH-

Initial (M) 1.0 X 10-2 0 0

Equilibrium (M) (1.00 X 10-2) - x x x

KH = Kb = [HOAc] [OH-]

nectoDue t
[OAc-]

39
 * Hyll + 120 >
-

NHy + 11-

a O O
initial (M) = 0 . 001

(
+ x + M

G x
N
= 0 001
. m - u

Kb :
5 ·
7 X10 -10
EXERCISES
Ka :

I
[HOAc] [OH-] X [H+] = Kw = 1.0 X 10-14
[OAc-] [H+] Ka 1.75 X 10-5
= 5.7 X 10-10

(x) (x) = 5.7 X 10-10

1.0 X 10-2 - x

Since CNaOAc > 100 Kb then x at the denominator is neglected

40
EXERCISES

kS7
(x) (x) = 5.7 X 10-10 77
1.0 X 10-2
x =  0.010 X (5.7 X 10-10)
= 2.4 X 10-6 M = [OH-]

pOH = - log (2.4 X 10-6)

= 5.62
pH = 14.00 - 5.62
= 8.38

From this example, if CA- is the concentration of the salt of the

weak acid and if x at the denominator can be neglected, then

x = [OH-] =  (Kw / Ka) CA- =  KbCA-

41
 EXERCISES

(2) Calculate the pH of NH4Cl with a concentration of o.10 M. Kb for

NH3 is 1.75 X 10-5.

NH4+ NH3 + H+

Initial (M) 0.10 0 0

Equilibrium (M) 0.10 - x x x

KH = Ka = [NH3] [H+] X [OH-] = Kw

[NH4+] [OH-] Kb

42
EXERCISES

[NH3] [H+] = Kw = 1.0 X 10-14

[NH4+] Ka 1.75 X 10-5
= 5.7 X 10-10

(x) (x) = 5.7 X 10-10

0.10 - x

x at the denominator is neglected since CNH4+ > 100 Ka

43
EXERCISES

(x) (x) = 5.7 X 10-10

0.10
x =  0.010 X (5.7 X 10-10)
= 7.6 X 10-6 M = [H+]

pH = - log (7.6 X 10-6)

= 5.12

From this example, if CBH+ is the concentration of the salt of a

weak base x at the denominator can be neglected, then

x = [H+] =  (Kw / Kb) CBH+ =  KaCBH+

44
BUFFER SOLUTIONS

A buffer solution is defined as solutions that resist change

in pH when the solution is diluted or when a small amount
of an acid or base is added
A buffer solution consists of a mixture of a weak acid and
its conjugate base (its salt) or mixture of a weak base and
its conjugate acid (its salt)
A buffer solution consists of a mixture of weak base and
its salt, or a mixture of weak base and its salt

45
BUFFER SOLUTION OF A WEAK
ACID

Example, buffer of a weak acid and its salt is acetic acid

and acetate salt

HOAc H+ + OAc-
Ka = [H+] [OAc-]
[HOAc]

Since OAc- ion is added (example from NaOAc), then [H+]

is not equal to [OAc-] and [H+] is then

46
BUFFER SOLUTION OF A WEAK
ACID

[H+] = Ka [HOAc]
[OAc-]
- log [H+] = - log Ka - log [HOAc]
[OAc-]
pH = pKa - log [HOAc]
[OAc-]
pH = pKa + log [OAc-]
[HOAc]

47
BUFFER SOLUTION OF A WEAK
ACID

This equation is known as Henderson Hesselbalch

equation
The general form of equation for a buffer solution of weak
acid (HB) and its salt (B-) can be written as
HB H+ + B -
pH = pKa + log [B-]
[HB]

or generally is written as
pH = pKa + log [acid salt]
[acid]
48
BUFFER SOLUTION OF A WEAK
ACID

Example, buffer of a weak base and its salt is NH3 and

NH4+

NH4+ NH3 + H+

Ka = [NH3] [H+] = Kw
[NH4+] Kb
[H+] = [NH4+] Ka = Kw [NH4+]
[NH3] Kb [NH3]

49
BUFFER SOLUTION OF A WEAK
ACID

- log [H+] = - log Ka - log [NH4+]

[NH3]
= - log Kw - log [NH4+]
Kb [NH3]

pH = pKa + log [NH3]

[NH4+]
= pKw - pKb - log [NH4+]
[NH3]

50
BUFFER SOLUTION OF A WEAK
ACID

Knowing pH + pOH = pKw

pH = (pH + pOH) - pKb - log [NH4+]
[NH3]
pOH = pKb - log [NH3]
[NH4+]
pOH = pKb + log [NH4+]
[NH3]

or generally is written as
pOH = pKb + log [base salt]
[base] 51
EXERCISES

(1) 1 L solution was prepared by mixing of 200 mL 0.25 M of acetic

acid (HA) with 300 mL 0.15 M of sodium hydroxide aqueous NaOH.
Given : Ka HA = 1.75 x 10-5. Calculate PH of solution produce

(a) Write the balance equation for this reaction.

HA + NaOH  NaA + H2O

(b) How many moles of H+ in excess?

# Initial mol number of HA
= 200 mL X 0.25 M
= 50 mmol
# Initial mol number of NaOH
= 300 mL X 0.15 M
= 45 mmol
52
EXERCISES

# From the balanced equation, 1 mol HA will react with 1

mol NaOH
# Excess mol of HA
= excess mol of H+
= 50 mmol - 45 mmol
= 5 mmol
= 5 X 10-3 mol

(c) How many moles of HA react, moles of NaOH used and moles
of salt formed?
# From the balanced equation
= Number of mol HA react
= Number of mol NaOH react
= Number of mol NaA formed
= 45 mmol = 45 x 10-3 mol
53
EXERCISES

(d) Calculate the pH of the final solution.

# pH = pKa + log [salt] / [acid]
= - log 1.75 X 10-5 + log (45 mmol / 5 mmol)
= 5.71

54
 EXERCISES

(2) Calculate the pH of a solution prepared by mixing 0.250 mol acetic

acid and 0.100 mol sodium acetate and diluted to 500 mL. What is
the pH when 10.0 mL of this solution is diluted to 500 mL? Ka for
acetic acid is 1.75 X 10-5

HOAc H+ + OAc-

pH = pKa + log [OAc-]

[HOAc]
= - log 1.75 X 10-5 + log (0.100 mol / 0.500 L)
(0.250 mol / 0.500 L)
= 4.36

55
EXERCISES

After dilution, the concentrations of acetic acid and sodium

acetate are

[HOAc] = 10.0 mL X 0.500 mmol / mL

500 mL
= 0.0100 M

[OAc-] = 10.0 mL X 0.200 mmol / mL

500 mL
= 0.00400 M

56
EXERCISES

pH = pKa + log [OAc-]

[HOAc]
= - log 1.75 X 10-5 + log (0.00400 M)
(0.0100 M)
= 4.36

57
 EXERCISES

(3) Calculate the pH of a solution that contains 0.10 M NH 4Cl and

0.10 M NH3. Kb for NH3 is 1.75 X 10-5

NH4+ NH3 + H+

pOH = pKb - log [NH3]

[NH4+]
= - log 1.75 X 10-5 - log (0.10)
(0.10)
= 4.76

pH = 14.00 - 4.76
= 9.24
58
INTRODUCTION TO ACID-BASE
TITRATION

Setup for titrating an acid with a base 59

INTRODUCTION TO ACID-BASE
TITRATION

60
INTRODUCTION TO ACID-BASE
TITRATION

61
INTRODUCTION TO ACID-BASE
TITRATION

62
INTRODUCTION TO ACID-BASE
TITRATION
Titrant
(strong acid/base)

Analyte
(weak/strong
acid/base)

Final condition occurred

in this Erlenmeyer flask 63
STANDARD SOLUTION

64
STANDARD SOLUTION

65
STANDARD SOLUTION

Exp. - Oxalic acid dihydrate (H2C2O4.2H20) vs NaOH

H2C2O4.2H20 fits the above criteria and therefore
may be used as a primary standard
NaOH absorbs water when it comes into contact
with air and therefore it is difficult to obtain a pure
and dry sample to weigh - > hydro scopic
.

For this reason, the NaOH solution will be titrated

with the oxalic acid standard to become a secondary
standard

66
STANDARD SOLUTION

67
STANDARD SOLUTION

Based on the complete reaction between the

analyte and a reagent

aA + tT  products

where
A and T = analyte and titrant
a and t = stoichiometric coefficients

68
STANDARD SOLUTION

HCl + NaOH  NaCl + H2O

H2SO4 + 2NaOH  Na2SO4 + 2H2O

Analyte Titrant
(2ndry standard)

H2C2O4 + 2NaOH  Na2C2O4 + 2H2O

Ultra pure Titrant

Mol HCl  mol NaOH
(primer (standardization – Mol H2SO4  2 mol NaOH
standard) find out the true Mol H2C2O4  2 mol
concentration) NaOH 69
 Exercise

A 25.00 mL analyte of HCl, H2SO4 and H2C2O4 was titrated with 0.10 M
NaOH separately. If the volume of NaOH required to completely react
with each analyte are HCl (12.50 mL), H2SO4 (25.00 mL) and H2C2O4
(10.00 mL), calculate the concentration of each analyte.

70
TITRATION CLASSIFICATIONS

Titration are often classified by the nature of this

titration reaction
 Acid-base titration - this titration is between
strong/weak acid and strong/weak base
 Complexometric titration – in this titration,
water soluble complex will be formed when
the analyte (a metal ion) reacts with the
titrant.
# The titrant here is a chelating agent
# e.g. : EthyleneDiamineTetraAcetic acid
(EDTA)

71
TITRATION CLASSIFICATIONS

 Oxidation-reduction (redox) titration – in this

titration, the reaction is between the
oxidizing and reducing agents
# oxidizing agent – gains electrons
# reducing agent – loses electrons
 Precipitation titration – in this titration,
insoluble product (precipitate) will be formed
when the analyte reacts with the titrant.
# e.g : AgCl (precipitate)

72
ACID-BASE TITRATION

Involves a neutralization reaction in which an acid is

reacted with an equivalent amount of base
Then end points of titration – can be detected by
constructing a titration curve
Titration curve – plotting the pH of the solution as a
function of the volume of titrant added
The titrant – always strong acid or a strong base
(always in burette)
Analyte – may be either a strong base/acid or a
weak acid/base (in Erlenmeyer flask)

73
ACID-BASE TITRATION

The equivalence point – the point in a titration when

the amount of added standard reagent is equivalent
to the amount of analyte
The end point – the point in a titration when a
physical change occurs that is associated with the
condition of chemical equivalence

74
STRONG ACID vs STRONG BASE

In this reaction, the titrant and the analyte ionize

completely since strong acid (Sa) and strong base
(Sb) dissociate completely
Three types of calculations must be done to
construct the hypothetical titration curve for
titrating a solution of strong acid with a strong base
Each calculation corresponds to a distinct stage in
the titration
# Pre - equivalence
# At equivalence
# Post - equivalence

75
STRONG ACID vs STRONG BASE
Pre – equivalence
# Base has been added but still not enough to
neutralize proton from acid
# Thus, the [H3O+] coming from acid excess

At equivalence
# Hydronium and hydroxide ions are present in
equal concentrations, and the hydronium ion
concentration is derived directly from ion- product
constant for water
Post – equivalence
# The analytical concentration of the excess
base is computed, and the hydroxide ion
concentration is assumed to be equal to or
multiple of the analytical concentration
76
 Exercise
Mettag .

Do the calculations needed to generate the hypothetical

titration curve for the titration of 50.00 mL of 0.0500 M
HCl with 0.1000 M KOH. Addition of KOH at 0.00, 20.00,
25.00 and 25.50 mL.

Last
HCl + KOH  KCl + H2O

1 mol HCl  1 mol KOH

hywery 77
Exercise

Pre – equivalence
# 0 mL addition of KOH

pH is based on HCl
HCl is a Sa

HCl will completely dissociate in water

HCl  H+ + Cl-
0.0500 M 0.0500 M

 pH = - log [H+]
= - log 0.0500 M = 1.30
78
Exercise

# 20 mL addition of KOH

mmol of HCl = 0.0500 mmol x 50.00 mL

mL
= 2.5 mmol

mmol of KOH = 0.1000 mmol x 20.00 mL

mL
= 2.0 mmol

= 2.5 mmol HCl – 2.0 mmol KOH

= 0.5 mmol HCl excess
79
 Exercise

HCl + KOH  KCl + H2 O

Initial 2.5 mmol 2.0 mmol 0 0
(Limiting
reagent)
Change - 2.0 mmol - 2.0 mmol + 2.0 mmol + 2.0 mmol
Equilibrium 0.5 mmol 0 2.0 mmol 2.0 mmol

[HCl] = 0.5 mmol

(50.00 + 20.00) mL
= 7.14 x 10-3 M

 pH = - log [H+]
= - log 7.14 x 10-3 M
= 2.15 80
Exercise

At equivalence
# 25.00 mL addition of KOH

mmol of HCl = 0.0500 mmol x 50.00 mL

mL
= 2.5 mmol

mmol of KOH = 0.1000 mmol x 25.00 mL

mL
= 2.5 mmol

81
 Exercise

HCl + KOH  KCl + H2 O

Initial 2.5 mmol 2.5 mmol 0 0
Change - 2.5 mmol - 2.5 mmol + 2.5 mmol + 2.5 mmol
Equilibrium 0 0 2.5 mmol 2.5 mmol

The equivalence point is reached

Since Sa and Sb are fully dissociated, the only equilibrium of concern is the
ionization of water

Kw = [H+][OH-]
= 1.0 x 10-14 M2
[H+] = [OH-] = 1.0 x 10-7 M

pH = - log [H+]
= 1 x 10-7 M
= 7.00 82
Exercise

Post – equivalence
# 25.50 mL addition of KOH

mmol of HCl = 0.0500 mmol x 50.00 mL

mL
= 2.5 mmol

mmol of KOH = 0.1000 mmol x 25.50 mL

mL
= 2.55 mmol

= 2.55 mmol KOH – 2.5 mmol HCl

= 0.05 mmol KOH excess
83
 Exercise

HCl + KOH KCl + H2 O

Initial 2.5 mmol 2.55 mmol 0 0
(Limiting
reagent)
Change - 2.5 mmol - 2.5 mmol + 2.5 mmol + 2.5 mmol
Equilibrium 0 0.05 mmol 2.5 mmol 2.5 mmol

[KOH] = 0.05 mmol

(50.00 + 25.50) mL
= 6.62 x 10-4 M

84
Exercise

KOH is a strong base and will fully dissociate

KOH  K+ + OH-

 pOH = - log [OH-]

= - log 6.62 x 10-4 M
= 3.18

pH + pOH = 14.00
pH = 14 - pOH
= 14 - 3.18
= 10.82

85
Exercise

(3) A 50.0 mL aliquot of 0.100 M HCl is titrated with

0.100 M NaOH. Calculate the pH of the solution after
the addition of 0, 5, 25, 50, 75 and 100 mL of NaOH.

(a) Additional of 0 mL NaOH - pH = 1.00

(b) Additional of 5 mL NaOH - pH = 1.09
(c) Additional of 25 mL NaOH - pH = 1.48
(d) Additional of 50 mL NaOH - pH = 7.00
(e) Additional of 75 mL NaOH - pH = 12.30
(f) Additional of 100 mL NaOH - pH = 12.52

- Please shows the titration curve obtained from the

pH values from each addition of NaOH above
86
 12

10

8
Equivalence point
pH =pH
7.00
6

20 40 60 80 100 120
V = 50Volume
mL NaOH (mL)

87
88
 WEAK ACID vs STRONG BASE

Stage Product or Reactant formed Final condition

Pre - equivalence Reactant Buffer solution
- Analyte excess (eg weak acid)
pH = pKa + log [salt]
Product [acid]
- Base Salt produced
At equivalence Reactant Salt hydrolyzed
- No more excess (base salt because from strong base)

Product [OH-] = √KhC = √ Kw C

- Base salt produced and water Ka

Post - equivalence Reactant Strong base excess

- Titrant excess (Eg strong base)
[OH-] from [base] excess.
Product
- Base salt produced and water [OH-] - CNaOH excess

89
Exercise

(4) Derive the titration curve for the titration of 20.0 mL

0.15 M formic acid (HCOOH) (Ka HCOOH 1.7 x 10-4)
with 0.25 M NaOH

HCOOH + NaOH  HCOONa + H2O

Determination the volume of NaOH at equivalent point.

90
Exercise
From stoichiometry :

mmol of NaOH = mol of HCOOH

= 20.0 mL x 0.15 mmol / mL
= 3 mmol

VNaOH required to complete the reaction

= mol/M
= 3 mmol of NaOH
0.25 mmol mL-1
= 12.00 mL

91
 Exercise

Pre – equivalence
# 0 mL addition of NaOH

only initial HCOOH in Erlenmeyer flask

So [H3O+] coming from dissociation of HCOOH

HCOOH is weak acid - so will partially dissociate

HCOOH + H2O HCOO- + H3O+

Initial (M) 0.15 0 0
Change (M) -x +x +x
Equilibrium (M) 0.15 - x x x

92
Exercise

Ka = [H3O+] [HCOO-]
If C/Ka > 100;
[HCOOH] so C-x ~ C

Ka = (x)(x) If C/Ka < 100;

(0.15 – x) so C-x  C

 x = [H3O+] =  (Ka x C)

Settle for x using

quadratic eq.
y = ax2 + bx + c
x = -b   (b2 – 4ac)
2a 93
 Exercise

# 8 mL addition of NaOH

HCOOH + NaOH HCOONa + H2O

Initial = 20.00 mL x = 8.00 mL x 0 0
0.15 mmol/mL 0.25 mmol/mL
= 3 mmol = 2 mmol
Change - 2 mmol - 2 mmol + 2 mmol + 2 mmol
(Limiting
reagent)
Equilibrium 1 mmol 0 2 mmol 2 mmol
Equilibrium = 1 mmol = 2 mmol
28.00 mL 28.00 mL
= 0.0357 M = 0.0714 M

94
Exercise

Final condition
- weak acid excess and its conjugate base (salt from strong
base and weak acid) produced so buffer solution is
formed

95
Exercise

Dissociation of weak acid

HCOOH + H2O HCOO- + H3O+
Initial (M) 0.0357 0.0714 0
Change (M) -x +x +x
Equilibrium (M) 0.0357 – x 0.0714 + x x

Dissociation of basic salt Common Ion

HCOONa  Na+ + HCOO- effect will
0.0714 0.0714 interrupt the
dissociation of
weak acid

96
Exercise

From equilibrium of weak acid (HCOOH)

Ka = [H3O+] [HCOO-]
If C/Ka > 100;
[HCOOH] so C-x ~ C

Ka = (x)(0.0714 + x) If C/Ka < 100;

(0.0357 – x) so C-x  C

 0.0714 + x  0.0714; and 0.0357 – x  0.0357, so

Ka = (x)(0.0714) or
(0.0357) pH = pKa + log [salt]
[acid]
x or [H3O+]  pH = ? 97
 Exercise

At equivalence
# 12 mL addition of NaOH
HCOOH + NaOH HCOONa + H2O
Initial = 20.00 mL x = 12.00 mL x 0 0
0.15 mmol/mL 0.25 mmol/mL
= 3 mmol = 3 mmol
Change - 3 mmol - 3 mmol + 3 mmol + 3 mmol
Equilibrium 0 0 3 mmol 3 mmol

Equilibrium = 3 mmol
32.00 mL
= 0.0938 M

98
Exercise

Only basic salt formed after reaction

Ion from weak
Dissociation of salt (complete) acid will act as
HCOONa  Na+ + HCOO- conjugate base
- 0.0938 0.0938 and will hydrolyze

99
Exercise

Salt hydrolyzed
HCOO- + H2O HCOOH + OH-
Initial (M) 0.0938 0 0
Change (M) -x +x +x
Equilibrium (M) 0.0938 – x x x

KH = Kb = Kw = [HCOOH][OH-] = (x)(x)
Ka [HCOO-] (0.0938 – x)

 x = [OH-] = Kw x C
Ka

100
 Exercise

Post equivalence
# 15 mL addition of NaOH
HCOOH + NaOH HCOONa + H2O
Initial = 20.00 mL x = 15.00 mL x 0 0
0.15 mmol/mL 0.25 mmol/mL
= 3 mmol = 3.75 mmol
Change - 3 mmol - 3 mmol + 3 mmol + 3 mmol
(Limiting
reagent)
Equilibrium 0 0.75 3 mmol 3 mmol

Equilibrium = 0.75 mmol = 3 mmol

35.00 mL 35.00 mL
= 0.0214 M = 0.0857 M
101
Exercise

Final condition
- base excess and basic salt produced

Dissociation of base (complete)

NaOH  Na+ + OH-
- 0.0214 M 0.0214 M

102
Exercise

Dissociation and hydrolyzed of basic salt

HCOONa  Na+ + HCOO-
- 0.0857 0.0857

HCOO- + H2O HCOOH + OH-

Initial (M) 0.0857 0 0.0214
Change (M) -x +x +x
Equilibrium (M) 0.0857 – x x 0.0214 + x

103
Exercise

OH- from salt hydrolyzed

KH = Kb = Kw = [HCOOH][OH-] = (x)(0.0214 + x)
Ka [HCOO-] (0.0857 – x)

Since Kh or Kb is too small; so

0.0857 - x ~ 0.0857 M
x + 0.0214 ~ 0.0214 M

Kw = (x)(0.0214) ; x = [OH-] from HCOONa = Kw (0.0857)

Ka (0.0857) Ka (0.0214)

104
Exercise

Total [OH-]
= [OH-] from NaOH + [OH-] from HCOONa
= 0.0214 M + 2.22 x 10-10 M
~ 0.0214 M

105
* HPr = Propionic Acid 106
107
Exercise

(5) How many milliliters of 0.150 M H2SO4 (sulfuric acid)

are required to react with 2.05 g of sodium hydrogen
carbonate, NaHCO3, according to the following
unbalanced equation?

H2SO4 (aq) + NaHCO3 (aq)

 Na2SO4 (aq) + H2O (l) + CO2 (g)

108
Solution E5

volume
grams of mol of stoic. mol of
of
NaHCO3 NaHCO3 conversion H2SO4
H2SO4

109
(6) A solution of hydrogen peroxide, H2O2, is titrated
with a solution of potassium permanganate, KMnO4.
The reaction is :

H2O2 (aq) + 2KMnO4 (aq) + H2SO4 (aq)

 O2 (g) + MnSO4 (aq) + K2SO4 (aq) + 2H2O (l)

It requires 46.9 mL of 0.145 M KMnO4 to titrate 20.0 g

of the solution of hydrogen peroxide. What is the
mass percentage of H2O2 in the solution ?

110
Solution E6

stoic. mol of H2O2 grams of

mol of KMnO4
conversion react H 2 O2

% of H2O2
= grams of H2O2 X 100
grams of solution of H2O2

111
(7) Calculate the pH of the solution that results when
40.0 mL of 0.100 M NH3 (Kb = 1.75 X 10-5) is :

(a) diluted with addition of 20.0 mL distilled water

(b) mixed with 20.0 mL of 0.200 M HCl solution
(c) mixed with 20.0 mL of 0.200 M NH4Cl solution
(d) mixed with 20.0 mL of 0.100 M HCl
(e) mixed with 20.0 mL of 0.250 M HCl

112
Solution E7

Step 1
Identify the process involved whether dilution, mixing
or reaction

Dissociation of basic salt

Calculate any information from the data given

113
 (a) Process – dilution
consistent mole, concentration decrease

M2 after dilution with Count [OH-] from

M 1 V1 = pOH 
addition of 20.0 mL partially dissociation
M 2 V2 pH
distilled water of NH3

114
 NH3 + H2 O NH4+ + OH-
Initial (M) C 0 0
Change (M) -x +x +x
Equilibrium (M) C-x x x

Kb = x2
C/Kb > 100 x = [OH-] = √ Kb x C
C-x

115
 (b) Process – acid base reaction

determine count excess reactant

calculate final
limiting reagent and amount of product
the mole condition
(LR) - depends on LR

116
At equivalence Acidic salt Salt
pH
point produced hydrolyzed

117
(c and d) Process – mixing
Weak base + its conjugate acid

Buffer pOH = pKb + log [salt]

solution [base]

118
 (e) Process – acid base reaction

count excess reactant and

calculate the determine limiting
amount of product - depends
mole reagent (LR)
on LR

119
 final HCl excess and basic salt
condition pH
(NH4Cl) produced

120
Equivalence points

It is important to note, that

the equivalence point pH is
7 ONLY for strong acid-strong
base reactions.

For every other acid-base reaction, the equivalence

point solution will contain ions or molecules that are
not spectators – so titration curves must be done
empirically to determine the equivalence point .
121
General rule

Strong Acid to Weak Base :

pH at equivalence point is always lower than 7

Strong Base to Weak Acid :

pH at equivalence point is always higher than 7

122
123
5.14 ACID-BASE INDICATORS

124
Thymol blue is an
unsuitable indicator
for this titration
because it changes
colour before the
equivalence point
(pH 7)

Alizarin yellow is also unsuitable because it changes colour

after the equivalence point

125
Bromothymol blue is suitable because its endpoint pH
of 6.8 (assume the middle of its pH range) closely
matches the reaction equivalence point pH of 7, and
the colour change is completely on the vertical
portion of the pH curve

126
THANK
YOU