Chemistry Grade 12 New Textbook

CHEMISTRY
CHEMISTRY
STUDENTS TEXTBOOK
CHEMISTRY
GRADE 12 Students Textbook
GRADE 12
STUDENTS TEXTBOOK
GRADE 12
FEDERAL DEMOCRATIC REPUBLIC OF ETHIOPIA MINSTRY OF EDUCATION FEDERAL DEMOCRATIC REPUBLIC OF ETHIOPIA MINSTRY OF EDUCATION
የኢትዮጵያ ፌደራላዊ ዴሞክራሲያዊ ሪፐብሊክ
የትምህርት ሚኒስቴር
FEDERAL DEMOCRATIC REPUBLIC OF ETHIOPIA
MINISTRY OF EDUCATION
CHEMISTRY
STUDENT TEXTBOOK
GRADE 12
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CHEMISTRY GRADE 12
CONTENTS
UNIT 1: ACID-BASE EQUILIBRIA
1.1 ACID-BASE CONCEPTS ...........................................................3

1.1.1 Arrhenius concept of acids and bases ...................................................3
1.1.2 Brønsted-Lowry Concept of Acids and Bases .......................................5
1.1.3 Lewis concept of acids and bases .......................................................... 11
1.2 IONIC EQUILIBRIA OF WEAK ACIDS AND BASES.......... 14
1.2.1 Ionization of water ................................................................................. 14
1.2.1 Measures of the strength of acids and bases in aqueous solution ....20
1.3 COMMON ION EFFECT AND BUFFER SOLUTION ..........28
1.3.1 The Common ion Effect ........................................................................28
1.3.2 Buffer Solutions ....................................................................................... 31
1.4 Hydrolsis of Salts ......................................................................35
1.4.1 Hydrolysis of Salts of Strong Acids and Strong Bases........................35
1.4.2 Hydrolysis of Salts of weak acids and strong bases ............................36
1.4.3 Hydrolysis of Salts of strong acids and weak bases ............................37
1.4.4 Hydrolysis of Salts of weak acids and week bases .............................37
1.5 Acid–Base Indicators and Titrations........................................38

1.5.1 Acid–Base Indicators..............................................................................38
1.5.2 Equivalents of Acids and Bases.............................................................40
1.5.3 Acid–Base Titrations ..............................................................................41
UNIT 2: ELECTRO CHEMISTRY
2.1 OXIDATION-REDUCTION REACTIONS............................50

2.1.1 Oxidation ................................................................................................50
2.1.2 Reduction ...............................................................................................51
2.1.3 Balancing Oxidation-Reduction (Redox) Reactions .........................52
2.2 ELECTROLYSIS OF AQUEOUS SOLUTIONS ...................... 57
2.2.1 Electrolytic cells .....................................................................................60
2.2.2 Preferential Discharge ...........................................................................62
2.2.3 Electrolysis of Some Selected Aqueous Solutions ...............................66
2.3 QUANTITATIVE ASPECTS OF ELECTROLYSIS .................72
2.3.1 Faraday’s First Law of Electrolysis ........................................................72
2.3.2 Faraday’s Second Law of Electrolysis ...................................................75
2.4 INDUSTRIAL APPLICATION OF ELECTROLYSIS ............. 76
2.5 VOLTAIC CELLS ...................................................................... 81
II
UNIT 3: INDUSTRIAL CHEMISTRY
3.1 Introduction ...........................................................................120

3.2 Natural Resources and Industry ............................................ 122
3.2.1 Natural resources (Raw materials) .....................................................122
3.2.2 Industry..................................................................................................123
3.3 Manufacturing of valuable products/ Chemicals .................. 125
3.3.1 Production of Ammonia (NH3) .........................................................126
3.3.2 Nitric Acid Manufacturing Process ...................................................133
3.3.3 Manufacturing of Sulphuric Acid .....................................................138
3.3.4 Nitrogen Based Fertilizers .................................................................. 141
3.3.5 Some Common Pesticide and Herbicides ........................................144
3.3.6 3.3.7 Manufacturing of Sodium Carbonate .....................................148
3.3.7 3.3.8 Manufacturing of Sodium Hydroxide NaOH .........................150
3.4 Some Manufacturing Industries in Ethiopia ........................ 152
3.4.1 3.4.1 Glass Manufacturing ..................................................................153
3.4.2 Manufacturing of Ceramics ...............................................................155
3.4.3 Cement ...................................................................................................157
3.4.4 3.4.4 Sugar Manufacturing ..................................................................159
3.4.5 Paper and Pulp ...................................................................................... 161
3.4.6 Tannery ..................................................................................................163
3.4.7 Food Processing and Preservation .....................................................164
3.4.8 Manufacturing of Alcoholic Beverages .............................................166
3.4.9 Soaps and Detergents ..........................................................................172
UNIT 4: POLYMER
4.1 Introduction to polymers........................................................ 184

4.2 Classification of Polymers ...................................................... 185
4.3 Polymerization Reactions ....................................................... 193
III
CHEMISTRY GRADE 12
UNIT 5: INTRODUCTION TO ENVIRONMENTAL
CHEMISTRY
5.1 Introduction ...........................................................................206

5.1.1 Components of the Environment ......................................................207
5.1.2 Natural Cycles in the Environment ................................................... 210
5.1.3 Concepts Related to Environmental Chemistry ...............................215
5.2 Environmental Pollution ....................................................... 216
5.2.1 Air Pollution .......................................................................................... 217
5.2.2 Water Pollution .....................................................................................220
5.2.3 Land Pollution.......................................................................................221
5.2.4 Pollutants of the Environment ............................................................223
5.3 Global Warming and Climate Change ..................................224

5.3.1 Global Warming and Climate Change .............................................224
5.3.2 Chemistry of Greenhouses Gasses and their effects on Climate
change ...............................................................................................226
5.4 Green Chemistry and Cleaner Production ...........................228
5.4.1 Principle of Green Chemistry .............................................................230
5.4.2 Cleaner production in chemistry ......................................................234
IV
Acid-Base Equilibria
UNIT 1
ACID-BASE EQUILIBRIA
Unit outcomes
At the end of this unit, you will be able to:

 describe the draw backs of Arrhenius,
 define Bronsted-Lowery &Lewis concepts of acids & bases
 describe the dissociation of water, weak mono-protic & polyprotic acids,
& weak bases;
 solve equilibrium problems involving concentration of reactants &
products, ka, kb, PH& POH
 discuss the common ion effect, buffer solution, hydrolysis of salts, acid-
base indicators and acid-base titrations
 explain how buffering action affects our daily lives using examples
 determine the equivalents of acid or base that are required to neutralize
specific amount of acid or base
 predict, in qualitative terms, whether a solution of a specific salt will be
acidic, basic or neutral
 explain how to solve problems involving concentration and pH of acid-
base titration
1
CHEMISTRY GRADE 12
Startup Activity
You have learnt the acid-base concepts and properties. Remember this and
discuss the following questions in group. After discussion write a report and
present to the class:
1. List the properties of acids and bases
2. What do you observe when the following indicators added in the solutions
listed in the table?
Color of indicator
Red Blue Phenol- Methyl
litmus litmus phthalein Orange
SOLUTION paper paper
acetic acid solution
hydrochloric acid solution
sodium chloride solution
ammonia solution
Lemon juice
The concepts of acids and bases are probably among the most familiar chemistry concepts.
The reason is that acids and bases have been used as laboratory chemicals for centuries, as
well as in the home. Common household acids include acetic acid ( CHCOOH , vinegar),
citric acid ( H 3C6 H 5O7 , in citrus fruits), and phosphoric acid ( H 3 PO4 , a flavoring in
carbonated beverages). Sodium hydroxide ( NaOH , drain cleaner) and ammonia ( NH 3 ,
glass cleaner), are household bases.
Weak acids and weak bases are important weak electrolytes. They are found in many
chemical and biological processes of interest. Amino acids, for example, are both weak
acids and weak bases. In this unit, we will learn some ways of expressing concentrations
of hydronium ions and of hydroxide ions in solutions of weak acids and weak bases. Then
you will examine equilibria involving these weak electrolytes. You will also see that the
indicators, used in titration, such as phenolphthalein, are weak acids or weak bases. Finally,
you will learn how to use these properties to select an appropriate indicator for a titration.
2
1.1 ACID-BASE CONCEPTS

At the end of this subunit, you will be able to:
 define acid by the Arrhenius concept
 define base by the Arrhenius concept
 Describe the drawbacks of Arrhenius concept
 define acid by the Bronsted-Lowry concept;
 give examples of Bronsted-Lowry acids
 define base by the Bronsted-Lowry concept
 give examples of Bronsted-Lowry bases.
 explain what conjugate acids and conjugate bases are
 identify the acid-base conjugate pairs from the given reaction;
 write an equation for self-ionization of water and ammonia.
 explain what is meant by amphiprotic species
 give examples of reactions of amphiprotic species;
 define acid by the Lewis concept
 give examples of Lewis acids
 define base by the Lewis concept
 give examples of Lewis bases
 calculate pH from  H +  and  H +  from pH calculate pOH from
OH −  and OH −  from pOH
1.1.1 Arrhenius concept of acids and bases
Activity 1.1
Form groups and discuss the following questions and write a report of your
discussion.
1. Explain Arrhenius acid and base concepts using suitable examples?
2. Does hydrogen ion exist freely in water?
3. What are the drawbacks of the Arrhenius’ concepts of acids and bases?
3
CHEMISTRY GRADE 12
The Swedish chemist Svante Arrhenius framed the first successful concept of acids and
bases. He defined acids and bases in terms of the effect these substances have on water.
According to Arrhenius, acids are substances that increase the concentration of H + (proton
ion) in aqueous solution, and bases increase the concentration of OH − (a hydroxide ion)
in aqueous solution.
In Arrhenius’s theory, a strong acid is a substance that completely ionizes in aqueous
solution to give H 3O + (aq) and an anion. An example is perchloric acid, HClO4

HClO4 (aq ) + H 2O(l ) → H 3O + (aq ) + ClO4 − (aq )
Other examples of strong acids are H 2 SO4 , HI , HBr , HCl , and HNO3 . A strong base
completely ionizes in aqueous solution to give OH − and a cation. Sodium hydroxide is an
example of a strong base.
NaOH ( s ) 
H 2O
→ Na + (aq ) + OH − (aq )
The principal strong bases are the hydroxides of Group IA elements and Group IIA elements
(except Be). Despite its early successes and continued usefulness, the Arrhenius theory
does have limitations.
Exercise 1.1
1. Based on their dissociations in water solution, classify each of the
following compounds as Arrhenius acid, Arrhenius base, or as a compound
that cannot be classified as an Arrhenius acid or Arrhenius base.
a.
HBr (aq ) + H 2O(l ) → H 3O + (aq ) + 2 Br − (aq )
b. NaCl ( s ) + H O(l ) → Na + (aq ) + Cl − (aq )
+ −
c. NH 3 (l ) + H 2O(l ) → NH 4 (aq ) + OH (aq )
+ −
2. NaOH (aq ) + H 2O(l ) → Na (aq ) + 2OH (aq )
4
1.1.2 Brønsted-Lowry Concept of Acids and Bases
Activity 1.2
From what you have learnt in Grade 10 chemistry, discuss the following
questions.
1. How does Brønsted-Lowry concept of acids and bases differ from
Arrhenius definition? What are the similarities?
2. Give two Brønsted-Lowry bases that are not Arrhenius bases.
3. Are there any Brønsted acids that do not behave as Arrhenius acids?
Consider the ionization of hydrochloric acid in water:
O
H + H Cl H H + Cl
O
H
H
Which one is a Brønsted-Lowry acid and which one is a Brønsted-Lowry basem?
In 1923, J. N. Brønsted in Denmark and T. M. Lowry in Great Britain independently
proposed a new acid base theory. They pointed out that acid–base reactions can be seen as
proton-transfer reactions and those acids and bases can be defined in terms of this proton
(H) transfer. According to their concept, an acid is a proton donor and a base is a proton
acceptor.
Let’s use the Brønsted–Lowry theory to describe the ionization of ammoniain aqueous
solution
In this reaction water acts as an acid. It gives up a proton (H+) to NH 3 , a base. As a
result of this transfer the polyatomic ions NH 4 + and OH − are formed- the same ions
produced by the ionization of the hypothetical NH 4OH of the Arrhenius theory.

However, they cannot be called Arrhenius bases since in aqueous solution they do
not dissociate to form OH − . The advantage of this definition is that it is not limited
to aqueous solutions. Bronsted-Lowry acids and bases always occur in pairs called
conjugate acid base pairs.
5
CHEMISTRY GRADE 12
1.1.2.1 Conjugate acid-base pairs
Conjugate acid-base pairs can be defined as an acid and its conjugate base or a base and its
conjugate acid. The conjugate base of a Brønsted-Lowry acid is the species that remains
when one proton has been removed from the acid. Conversely, a conjugate acid results
from the addition of a proton to a Brønsted-Lowry base. Every Brønsted-Lowry acid has
a conjugate base, and every Brønsted- Lowry base has a conjugate acid. For example,
the chloride ion (Cl − ) is the conjugate base formed from the acid HCl , and H 2O is the
conjugate base of the acid H 3O + . Similarly, the ionization of acetic acid can be represented
as
Conjugate acid - base pair
CH 3COOH (aq )+ H 2O(l )  CH 3COO − (aq ) + H 3O + (aq )

Acid Base Base Acid
Conjugate acid - base pair
In the above reaction, CH 3COOH acts as an acid. It gives up a proton, H + , which is taken
up by H 2O . Thus, H 2O acts as a base. In the reverse reaction, the hydronium ion, H 3O +
, acts as an acid and CH COO − acts as a base. When CH 3COOH loses a proton, it is
converted into CH 3COO − . Notice that the formulas of these two species differ by a single
proton, H + . Species that differ by a single proton ( H + ) constitute a conjugate acid–base
pair. Within this pair, the species with the added H + is the acid, and the species without the
H + is the base..For any conjugate acid-base pair,
 The conjugate base has one fewer H and one more minus charge than the acid.
 The conjugate acid has one more H and one fewer minus charge than the base.
6
Table 1.1: The conjugate pairs in some Acid-Base Reactions.
Conjugate pair
Acid + Base ⇌ Base + Acid
Conjugate pair
HF + H 2O F- + H3O+
HCOOH + CN- HCOO- + HCN
NH4+ + CO32- NH3 + HCO3-
H2PO4- + OH- HPO4- + H 2O
H2SO4 + N 2H 5+ HSO4- + N2H62+
HPO42- + SO32- PO43- + HSO3-
Example 1.1
For each of the following reactions, which occur in aqueous solution, identify
the Brønsted-Lowry acids and bases and their respective conjugates in each of
the following reactions.
a. NH 3 + H 2 PO4 −  NH 4 + + HPO4 2 −
b. HCl + H 2 PO4 −  Cl − + H 3 PO4
Solution:
To identify Brønsted-Lowry acids and bases, we look for the proton donors and
proton-acceptors in each reaction.
a. H 2 PO4 − is converted to HPO4 2 − by donating a proton. So, H 2 PO4 − is an acid,
and HPO4 2 − is its conjugate base. NH 3 accepts the proton lost by the H 2 PO4 −
.As a result, NH 3 is a base, and NH 4 + is its conjugate acid.
NH 3 + H 2 PO4 −  NH 4 + + HPO4 2−
Base Acid Acid Base
b H 2 PO4 − accepts a proton from HCl . Therefore, H 2 PO4 − is a base and H 3 PO4
is its conjugate acid. HCl donates a proton to H 2 PO4 − . Thus, HCl is an acid,
and Cl − is its conjugate base
HCl + H 2 PO4 −  Cl − + H 3 PO4

Acid Base Base Acid
7
CHEMISTRY GRADE 12
Exercise 1.2
1. Identify the Brønsted-Lowry acids, bases, conjugate acids and conjugate
bases in each of the following reaction
− +
b. HClO2 + H 2O  ClO2 + H 3O
− −
c. OCl + H 2O  HOCl + OH
2− − −
d. H 2O + SO3  OH + HSO3
Strengths of Conjugate Acid-Base Pairs
How do you know the strengths of conjugate acid- base pairs?
The net direction of an acid-base reaction depends on relative acid and base strengths: A
reaction proceeds to the greater extent in the direction in which a stronger acid and stronger
base form a weaker acid and weaker base. The stronger the acid, the weaker is its conjugate
base. Similarly, the stronger the base, the weaker is its conjugate acid. For example, HCl
is a strong acid, and its conjugate base Cl − , is a weak base. Acetic acid, CH 3COOH , is a
weak acid, and its conjugate base, CH 3COO − ,is a strong base. The following chart shows
the strength of conjugate acid-base pairs.
8
Chart 1.1: Strengths of Conjugate Acid-Base Pairs.
9
CHEMISTRY GRADE 12
1.1.2.2 Auto ionization of substances
Name the ions present in water. How are they formed?
Molecular auto ionization (or self-ionization) is a reaction between two identical neutral
molecules, especially in a solution, to produce an anion and a cation. If a pure liquid partially
dissociates into ions, it is said to be self-ionizing. Water, as we know, is a unique solvent.
One of its special properties is its ability to act either as an acid or as a base. Water functions
as a base in reactions with acids such as HCl and CH 3COOH , and it functions as an acid
in reactions with bases such as NH 3 . Water is a very weak electrolyte and therefore a poor
conductor of electricity, but it does undergo ionization to a small extent:
2 H 2O(l )  H 3O + (aq ) + OH − (aq )
H
H
O H O H
O H + O H
H
H Base
Base Acid Acid
This reaction is sometimes called the auto ionization of water. Note that, in this reaction,
some water molecules behave as acids, donating protons, while the other water molecules
behave as bases, accepting protons.
1.1.2.3 Amphiprotic Species
Do you think that a molecule or an ion can be both a donor or acceptor of protons?
Molecules or ions that can either donate or accept a proton, depending on the other reactant,
are called amphiprotic species. For example, HCO3− acts as an acid in the presence of
OH − but as a base in the presence of HF . The most important amphiprotic species is water
itself. When an acid donates a proton to water, the water molecule is a proton acceptor,
and hence a base. Conversely, when a base reacts with water, a water molecule donates a
proton, and hence acts as an acid. Consider, for example, the reactions of water with the
base NH 3 and with the acid CH 3COOH (acetic acid)
10
-
NH3(aq) + H 2O(l) NH4+(aq) + OH (aq)
acid acid base
base
-
H C2H3O2(aq) + H2O(aq) C2H3O2 (aq) + H3O+(aq)
acid base base acid
In the first case, water reacts as an acid with the base NH 3 . In the second case, water
reacts as a base with the acid CH 3COOH .
Exercise 1.3
1. Define each of the following terms and give examples for each.
a. autoionization b. amphiprotic species
2. Write equations to show the amphiprotic behavior of
a H 2 PO4 − b. H 2O
3. Predict the relative strengths of each of the following groups:
− −
a. OH − , Cl − , NO , CH 3COO , and NH 3
b. HClO4 , CH 3COOH , HNO3 and HCl
3. What is the weakness of the Brønsted-Lowry acids and bases theory?
4. Write the self-ionization of ammonia.
1.1.3 Lewis concept of acids and bases
Activity 1.3
Form groups and discuss the following questions and report the result of
your discussion to your teacher.
1. What is the main difference between Lewis acid -base and Brønsted-
Lowry acid - base concepts?
2. Are all Brønsted-Lowry acids and bases are also acids and bases
according to Lewis concept?
3. Is there any limitation to the Brønsted-Lowry definition of acids and
bases? Explain if any
11
CHEMISTRY GRADE 12
G. N. Lewis, who proposed the electron-pair theory of covalent bonding, realized that the
concept of acids and bases could be generalized to include reactions of acidic and basic
oxides and many other reactions, as well as proton-transfer reactions. According to this
concept, the Lewis acid-base definition holds that
 A base is any species that donates an electron pair to form a bond.

 An acidis any species that accepts an electron pair to form a bond.
Consider, for example, the reaction of boron trifluoride with ammonia
H F H
F
+ N H F B N H
B F
H F H
F
Lewis acid Lewis base
The boron atom in boron trifluoride, BF3 , has only six electrons in its valance shell and
needs two electrons to satisfy the octet rule. Consequently, BF3 (Lewis acid) accepts a
pair of electrons from NH 3 (Lewis base). This example suggests that in a Lewis acid-base
reaction, we should look for:
1. a species that has an available empty orbital to accommodate an electron pair such
as the B atom in BF3 , and
2. a species that has lone-pair electrons such as N in NH 3

The Lewis definition allows us to consider typical Brønsted-Lowry bases, such as
OH − , NH 3 , and H 2O , as Lewis bases. They all have electron pairs available to
donate for electron-deficient species. Note that any molecule or negatively charged
species having an excess of electrons can be considered as a Lewis base, and any
electron-deficient molecule or positively charged species can be considered as a
Lewis acid.
12
Example 1.2
1. Identify the acid and the base in each Lewis acid–base reaction.
BH 3 + (CH 3 ) 2 S → H 3 BS (CH 3 ) 2
CaO + CO2 → CaCO3
BeCl2 + 2Cl − → BeCl4 2−
Solution:
In BH 3 , boron has only six valence electrons. It is therefore electron deficient and
can accept a lone pair of electrons. Like oxygen, the sulfur atom in (CH 3 ) 2 S has
two lone pairs. Thus (CH 3 ) 2 S donates an electron pair on sulfur to the boron atom
of BH 3 . The Lewis base is (CH 3 ) 2 S , and the Lewis acid is BH 3 .
CO2 accepts a pair of electrons from the O 2− ion in CaO to form the carbonate
ion. The oxygen in CaO is an electron-pair donor, so CaO is the Lewis base.
Carbon accepts a pair of electrons, so CO2 is the Lewis acid.
The chloride ion contains four lone pairs. In this reaction, each chloride ion
donates one lone pair to BeCl2 , which has only four electrons around Be . Thus,
the chloride ions are Lewis bases, and BeCl2 is the Lewis acid.
2. Identify the acid and the base in each Lewis acid–base reaction.
(CH 3 ) 2 O + BF3 → (CH 3 ) 2 O : BF3
H 2O + SO3 → H 2 SO4
Solution
Lewis’s base: (CH 3 ) 2 O ; Lewis’s acid: BF3
Lewis’s base: H 2O ; Lewis’s acid: SO3
Exercise 1.4
1. Identify Lewis acids and Lewis bases in each of the following reactions.
a. H + + OH −  H 2O
b. Cl − + BCl3  BCl4 −
c. K + + 6 H 2O  K ( H 2O)6 +
d. OH − + Al (OH )3  Al (OH ) 4 −
e. CO2 + H 2O  H 2CO3
f. Ni + 4CO  Ni (CO) 4
13
CHEMISTRY GRADE 12
1.2 IONIC EQUILIBRIA OF WEAK ACIDS AND BASES

 describe the ionization of water;
 derive the expression of ion product for water, K w

 explain why water is a weak electrolyte;
 use K w to calculate  H 3O +  or OH −  in aqueous solution;

 write an expression for the percent ionization of weak acids or weak
bases;
 calculate the percent dissociation of weak acids and bases;
 write the expression for the acid-dissociation constant, K a ;
 calculate K a for an acid from the concentration of a given solution and

it’s pH ;
 calculate  H +  and pH of an acidic solution from given values of K a

and the initial concentration of the solution;
 write the expression for the base-dissociation constant, K b ;
 calculate K b for a base from the concentration of a basic solution and its
pOH ; and
OH − 
 calculate the and pOH of a basic solution from a given value of
K b and the initial concentration of the solution.
1.2.1 Ionization of water
How do you calculate the concentration of H 3O + ions if the concentrations of OH − ions

and K w at 25°C are given?
Although pure water is often considered a non-electrolyte (nonconductor of electricity),

precise measurements do show a very small conduction. This conduction results from
self-ionization (or autoionization) of water, a reaction in which two like molecules react
to give ions. The H 2O molecule can act as either an acid or a base; it is amphiprotic. It
should come as no surprise that amongst themselves water molecules can produce H 3O +
and OH − ions via the following self-ionization reaction or autoionization reaction:
14
H 2O(l ) + H 2O(l )  H 3O + (aq ) + OH − (aq )
Like any equilibrium process, the auto-ionization of water is described quantitatively by

an equilibrium constant:
 H 3O +  OH − 
Kc =
[ H 2O ]
2
Because the concentration of ions formed is very small and the concentration of H 2O
remains essentially constant, about 56 Mat 25oC, we multiply Kc by [ H 2O ] to obtain a

2
new equilibrium constant, the ion-product constant for water, K w :
[ H 2=
O] Kc =  H 3O +  OH − 
2
constant
We call the equilibrium value of the ion product  H 3O +  OH −  , the ion-product constant
for water, K w . At 25oC, the value of K w is 1.0 x 10-14. Like any equilibrium constant, K w
varies with temperature. At body temperature (37oC), K w equals 2.5 x 10-14.
=K w =
H 3O +  OH −  1.0 x 10−14 at 25 oC
Because we often write H + (aq ) for H 3O + (aq ) , the ion-product constant for water can be
written
K w =  H 3O +  OH − 
Using K w , you can calculate the concentrations of H 3O + and OH − ions in pure water.
These ions are produced in equal numbers in pure water, so their concentrations are equal.
Let x =
= H 3O +  OH −  . Then, substituting into the equation for the ion-product
constant, K w =  H 3O +  OH −  you get at 25 oC, 1.0 x 10-14 = x2 hence x equals 1.0 x 10-7.
Thus, the concentrations of H O + and OH − are both 1.0 x 10 -7 M in pure water.
If you add an acid or a base to water, the concentrations of H 3O + and OH − will no longer
be equal. The equilibrium-constant equation K w =  H 3O +  OH −  will still hold.
15
CHEMISTRY GRADE 12
In any aqueous solution at 25°C, no matter what it contains, the product of  H +  and
OH −  must always equal 1.0 × 10–14.

The equilibrium nature of auto-ionization allows us to define “acidic” and “basic” solutions
in terms of relative magnitudes of  H 3O +  and OH −  :
i. a neutral solution, where  H 3O +  = OH −  .
ii. an acidic solution, where  H 3O +  > OH −  .
iii. a basic solution, where OH −  >  H 3O + 
Activity 1.4
Form a group and discuss the following. Write a report on the discussion and
present to the class. Many substances undergo auto-ionization in analogous
to water. For example, the auto-ionization of liquid ammonia is:–
2NH 3  NH 4 + + NH 2 −
a. Write K c expression for auto-ionization of ammonia that is analogous
to the K w expression for water.
b. Name the strongest acids and strongest bases that can exist in liquid
ammonia?
c. For water, a solution with OH −  <  H 3O +  is acidic. What are the
analogous relationships in liquid ammonia?
Example 1.3
A research chemist adds a measured amount of HCl gas to pure water at 25 0Cand
obtains a solution with  H O 

+ -4
 = 3.0 x 10 M. Calculate OH − 
. Is the solution neutral,
acidic, or basic?
Solution: We use the known value of K w at 25 0C (1.0 x 10─14) and the given
 H 3O +  (3.0x10-4M) to solve for OH −  . Then we compare  H 3O +  with OH − 
to determine whether the solution is acidic, basic, or neutral
Kw 1.0 x 10−14
OH − 
Calculate for the= = = −4
3.3 x 10−11 M
 H 3O 
+
3.0 x 10
Because  H 3O +  > OH −  , the solution is acidic
16
Exercise 1.5
1. Calculate  H +  or OH −  , as required, for each of the following solutions
at 25°C,and state whether the solution is neutral, acidic, or basic.
a.  H +  = 1.0 x 10−7 M b. OH −  = 1.0 x 10−4 M
c . OH −  = 1.0 x 10−8 M
2. Calculate the concentration of OH − in a solution in which
a.  H 3O +  = 2.0 x 10−5 M b.  H 3O +  = OH − 
c.  H 3O +  = 102 x OH − 
3. Calculate  H 3O +  in a solution that is at 25°C and has OH −  = 6.7 x 10−2 M
. Is the solution neutral, acidic, or basic?
4. At 40°C, the value of K w is 2.92 × 10–14. Calculate the  H +  and OH − 
of pure water at 40°C.
5. Why water is a weak electrolyte?
The pH scales
It is a well-known fact that whether an aqueous solution is acidic, neutral, or basic
depends on the hydronium-ion concentration. You can quantitatively describe the acidity
by giving the hydronium-ion concentration. But because these concentration values may
be very small, it is often more convenient to give the acidity in terms of pH , which is
defined as the negative of the logarithm of the molar hydronium-ion concentration. pH
is a measure of the hydronium ion content of a solution. It is also restated in terms of
 H 3O +  .
− log  H 3O +  or pH =
pH = − log  H + 
Thus, in a solution that has  H 3O +  = 2.5 x 10−3 M
− log(2.5 x 10−3 ) =
pH = 2.60
Note that the negative logarithm gives us positive numbers for pH . Like the equilibrium
constant, the pH of a solution is a dimensionless quantity.
To determine the  H 3O +  , that corresponds to a particular pH value, we do an inverse

calculation. In a solution with pH = 4.5,
log  H 3O +  = − 4.50 and  H 3O +  =10−4.50 = 3.2 x 10−5 M

The pH of a solution is measured by a pH - meter.
17
CHEMISTRY GRADE 12
Figure 1.1: pH -meter.

A pH meter is commonly used in the laboratory to determine the pH of a solution.
Although many pH meters have scales marked with values from 1 to 14, pH values
can, in fact, be less than1 and greater than 14.
pH value decreases as the concentration of H + ions increase; in other words, the more
acidic the solution, the lower its pH ; the more basic the solution, the higher its pH .
For a neutral solution, pH = 7 Acidic solutions have pH < 7 Basic solutions have
pH > 7
Activity 1.5
In your group, measure the pH of the following substances, using a pH-meter.
Copy and fill in the following table. Compare your results with those of other
groups. Find the pH values of the substances in reference books and other
sources and compare your results with the values you observed.
Substance Acidic, Basic or Neutral

pH
Beer
Milk of magnesia
Tomato juice
Lemon juice
Drinking water
18
The pH notation has been extended to other exponential quantities. A pOH scale
analogous to the pH scale can be devised using the negative logarithm of the hydroxide
ion concentration of a solution. Thus, we define pOH as:
pOH = − log OH − 

If we are given the pOH value of a solution and asked to calculate the OH − ion
concentration, we can take the antilog of the above equation as follows
OH −  = 10− pOH

Another useful expression can be derived by taking the negative logarithmof the
expression (written for 25 °C) and introducing the symbol pK w = − log K w . Now
=
consider again the ion product for water at 25°C. K w =
H 3O +  OH −  1.0 x 10−14
Taking the negative logarithm of both sides, we obtain
- (log  H 3O +  + log OH -  ) =

- log(1.0 x 10-14 )
− log  H 3O +  = − log OH −  =

14
From the definition of pH and pOH we obtain: pH + pOH =
14
Thus, in general, the sum of the pH and pOH values must equal pK w . This equation
provides us with another way to express the relationship between the H + ion concentration
and the OH − - ion concentration.
Example 1.4
Calculate:
a. the pH and pOH of a juice solution in which  H 3O +  is 5.0 ×10–3 M
b. the  H 3O +  and OH −  of human blood at pH = 7.40
Solution:
 H 3O +  = 5.0 x 10−3 M
a.
= pH ?= and pOH ?
pH = − log  H 3O +  = − log(5.0 x 10−3 )
= 3 − log 5.0 =2.3
pH + pOH =
14
pOH= 14 − pH
pOH= 14 − 2.3
19
CHEMISTRY GRADE 12
= 11.7
b. pH =7.40, pOH =
14 − 7.40 =6.6
 H 3O +  ?=
= OH −  ?
pH = − log  H 3O +  and pOH =
− log[OH − ]
log  H 3O +  =
−7.40 and log[OH − ] =
−6.6
 H 3O=
+
 10−=
7.40
4.0 x 10−8 M and [OH
= −
=
] 10 −6.6
2.51 x 10−7 M
Exercise 1.6
1. A solution formed by dissolving an antacid tablet has a pH of 9.18 at
25°C. Calculate
 H + 
,
OH −  and pOH .
A solution is prepared by diluting concentrated HNO3 to 2.0 M, 0.30 M and

0.0063 M HNO3 at 25°C. Calculate  H +  , OH −  , pH and pOH of the
three solutions.
1.2.1 Measures of the strength of acids and bases in

aqueous solution
The strength of acids and bases depends on a number of factors. Some of the ways to
compare the strengths of acids and bases are the concentration of hydrogen and hydroxide
ions, pH and pOH , percent dissociation, K a and K b for the reaction describing its
ionization in water.
1.2.1.4 Concentration of hydrogen and hydroxide ions
How do the concentration of hydrogen and hydroxide ions affect acid and base strength?
By definition a strong acid is one that completely dissociates in water to release proton. In
solutions of the same concentration, stronger acids ionize to a greater extent, and so yield
higher concentrations of hydronium ions ( H 3O + ) than do weaker acids. Examples of the
strong acids are: hydrochloric acid ( HCl ) , nitric acid ( HNO3 ) , perchloric acid ( HClO4 )
, and sulfuric acid ( H 2 SO4 ) . Each of these acids ionize essentially 100% in solution. By
contrast, however, a weak acid, being less willing to donate its proton, will only partially
20
dissociate in solution. Base strength refers to the ability of a base to accept protons. A
strong base accepts more protons readily than a weak base. A solution of a stronger base
will contain a larger concentration of hydroxide ions than a solution of a weaker base if
both solutions are of equal concentration.
The net direction of an acid-base reaction depends on relative acid and base strengths: a
reaction proceeds to the greater extent in the direction in which a stronger acid and stronger
base form a weaker acid and weaker base.
Activity 1.6
By referring to this text book and other chemistry books, list strong acids,
strong bases, weak acids and weak bases. Then discuss what you have written
with the rest of the class. What is the reason of your classification of acids
and bases as strong and weak?
1.2.1.5 pH and pOH
If the pH of a solution at 25°C is 2, is it acidic, neutral or basic?

One way to determine the strength of acids is using the pH values. The smaller the pH
value, the stronger the acid. The concentration of hydroxide ions in a solution can be
expressed in terms of the pOH of the solution. Hence, the strength of bases can also be
determined from their pOH values. The smaller the pOH value, the stronger the base.
1.2.1.6 Percent Ionization
How is the percent ionization and acid strength related?

Another measure of the strength of an acid is its percent ionization, which is defined asthe
proportion of ionized molecules on a percentage basis. Mathematically:
Ionized acid concentration at equilibrium

Percent ionization = x 100 %
Initial concentration of acid
The strength of an acid depends on the percentage of the acid molecules that dissociate
inwater solution. The stronger the acid, the greater the percent ionization.Strong acids and
strong bases ionize nearly completely in water. But weak acids and weak bases dissociate
partially in water, and their percent of ionization is small.
21
CHEMISTRY GRADE 12
1.2.1.7 Dissociation (Ionization) Constants
Acid ionization Constant, K a
What is the relationship between strength of acids with their acid-dissociation constant
values?
The acid Ionization constant or dissociation constant is a quantitative measure of the

strength of an acid in solution. It is the equilibrium constant for the reaction of dissociation
of acid into its conjugate base and hydrogen ion. Acid dissociation constant of weak acid
HA like acetic acid, formic acid can be written as:
HA(aq ) + H 2O(l )  H 3O + (aq ) + A− (aq )

the dissociation-constant expression can be written as:
 H 3O +   A− 
K=
[ H 2O ][ HA]
Since the concentration of water is nearly constant, we can write;
 H 3O +   A− 
K [ H 2O ] =
[ HA]
The product of the two constants, K and [ H 2O ] , is itself a constant. It is designated as Ka,
which is the acid-dissociation constant or the acid-ionization constant. Hence for a weak
acid, HA :
 H 3O +   A− 
Ka =
[ HA]
Acids are classified as either strong or weak, based on their ionization in water. Therefore,
the numerical value of K a is a reflection of the strength of the acid. Acids with relatively
higher K a values are stronger than acids with relatively lower K a values. The ionization-
constants of some weak monoprotic acids are tabulated in table 1.2
22
Table 1.2: Ionization constant of some weak monoprotic acids at 25°C.

Name of the Acid Formula Ka
Acetic acid CH 3COOH 1.8 × 10–5
Ascorbic acid C6 H 8O6 8.0 × 10–5
Benzoic Acid C6 H 5COOH 6.5 × 10–5

Formic acid HCOOH 1.7 × 10–4
Hydrocyanic acid HCN 4.9 × 10–10
Hydrofluoric acid HF 6.8 × 10–4
Hypobromous acid HOBr 2.5 × 10–9
Hypochlorous acid HOCl 3.0 × 10–8
Nitrous acid HNO2 4.5 × 10–4
Example 1.5
1. A 0.250 M aqueous solution of butyric acid is found to have a pH of 2.72.
Determine K a for butyric acid
Solution:
CH 3 (CH 2 ) 2 COOH (aq ) + H 2O(l )  H 3O + (aq ) + CH 3 (CH 2 ) 2 COO − (aq )
Initial conc. 0.250 M ------- -------
Changes −x +x +x
equilib. conc. 0.250 M − x x x
x is a known quantity, It is the  H 3O  in solution, which we can determine
+
from the pH .
log  H 3O +  =
− pH =
−2.72
 H= +
3O 
 10
= −2.72
1.9 x 10−3 M
Now we can solve the following expression for K w by substituting in the value x
= 1.9 x 10 -3 M
(1.9 x 10−3 )(1.9 x 10−3 )
=Ka = −3
1.5 x 10−5
0.250 − 1.9 x 10
2. Calculate the pH of a 0.50 M HF solution at 25°C. The ionization of HF is
given by
HF (aq ) + H 2O(l )  H 3O + (aq ) + F − (aq )
Solution: The species that can affect the pH of the solution are HF , and the
conjugate base F − , Let x be the equilibrium concentration of H 3O +
and F − ions in molarity (M). Thus,
23
CHEMISTRY GRADE 12
HF (aq ) + H 2O(l )  H 3O + (aq ) + F − (aq )

Initial conc. 0.50 ----- -----
Changes −x +x +x
Equil. conc. 0.50 − x x x
 H 3O +   F − 
Ka = 
[ HF ]
Substituting the concentration of HF , H+ and F − , in terms of x, gives:
( x)( x)
=Ka = 6.8 x 10−4
0.50 − x
Rearranging this expression provides:
x2 + (6.8 × 10–4 ) x – 3.4 × 10–4 = 0
This is a quadratic equation that can be solved, using the quadratic formula, or
youcan use the approximation method for x. Because HF is a weak acid, and
weak acids ionize only to a slight extent, x must be small compared to 0.50.
Therefore, you can make this approximation: 0.50 − x ≈ 0.50
Now, the ionization constant expression becomes
x2 x2
≈ = 6.8 x 10−4
0.50 − x 0.50
Rearranging this equation gives:
= =
x 2 (0.50)(6.8 x 10−4 ) 3.4 x 10−4
=x 3.4 x 10−4 1.8 x 10−2 M
=
Thus, we have solved for x without using the quadratic equation. At equilibrium,
we have
[ HF ] =
(0.50 − 0.018) M =
0.48 M
=  F −  =
H 3O +  0.018 M
and the pH of the solution is
pH =
− log(0.018) =
1.74
How good is this approximation? Because K a values for weak acids are generally
known to an accuracy of only ± 5%, it is reasonable to require x to be less
than 5 % of 0.50, the number from which it is subtracted. In other words, the
approximation is valid if the percent ionization is equal to or less than 5%.
0.018
x 100 % = 3.6 % Is the approximation valid?
0.50
24
Example: 1.6
1. Only a small fraction of a weak acid ionizes in aqueous solution. What is the
percent ionization of
acetic acid in a 0.100M solution of acetic acid, CH 3COOH ?

Solution:
CH 3COOH (aq ) + H 2O(l )  H 3O + (aq ) + CH 3COO − (aq ), K a =
1.8 x 10−5
Initial conc. 0.100 M ----- -----
Changes -x +x +x
Equilib conc. 0.100 M - x x x
x is a known quantity, it is  H 3O +  in solution, which we can determine from
the K a
 H 3O +  CH 3COO − 
Ka =
[CH 3COOH ]
Substituting the concentration of CH 3COOH , H 3O + and CH 3COO − , in terms of

x, gives:
( x)( x)
Ka =
(0.100 − x)
−5 x2
1.8 x 10 =
0.100 − x
Since CH 3COOH is a weak acid, and weak acids ionize only to a slight extent, x
must be small compared to 0.10. Therefore, you can make the approximation:
0.10 − x ≈ 0.10 .
Now, the equation becomes (1.8 x 10−5 )(0.100) = x 2
=x 1.8 x 10−6 1.342 x 10−3

=
1.342 x 10−3
=
Percent ionization = x 100 % 1.342 %
0.100
How do you calculate the pH of weak acids?

Generally, we can calculate the hydrogen-ion concentration or pH of an acid solution at
equilibrium, given the initial concentration of the acid and its K a value.
25
CHEMISTRY GRADE 12
Exercise 1.7
Calculate the percent ionization of a 0.10M solution of acetic acid with a
pH of 2.89.
Calculate the pH of a 0.10 M solution of acetic acid. Ka = 1.8 x 10-5
For a 0.036 MHNO 2 solution.
a. Write a chemical equation that shows the ionization of nitrous acid in water.
b. Calculate the equilibrium concentration of hydrogen ions and nitrous
acid at 25°C, using the approximation method. Then check whether the
approximation is valid or not.
c. If the approximation is invalid, use the quadratic formula to calculate the
concentration of hydrogenions.
d. Calculate the pH of the solution.
Base dissociation constant, K b

Equilibria involving weak bases are treated similarly to those for weak acids. Ammonia,
for example, ionizes in water as follows:
NH 3 (aq ) + H 2O(l )  NH 4 + (aq ) + OH − (aq )

The corresponding equilibrium constant is:
 NH 4 +  OH − 
Kc =
[ NH 3 ][ H 2O ]
Because the concentration of H 2O is nearly constant, you can rearrange this equation as
you did for acid ionization.
 NH 4 +  OH − 
= c[
K b K= H 2 ]
O
[ NH 3 ]
where K b is the base dissociation constant.
In general, a weak base B with the base ionization
B (aq ) + H 2O(l )  HB + (aq ) + OH − (aq )
has a base-ionization constant, K b (the equilibrium constant for the ionization of a weak
base), equal to:
 HB +  OH − 
Kb =
[ B]
Note that K b values for strong bases are large, while K b values for weak bases are small.
26
Table 1.3: shows the K b values of some common weak bases at 25°C
Base Formula
Kb
Ammonia 1.8 × 10–5
NH 3
Aniline 4.0 × 10–10
C6 H 5 NH 2
Ethylamine 4.7 × 10–4
C2 H 5 NH 2
Hydrazine 1.7 × 10–6
C2 H 4
Hydroxylamine 1.1 × 10–6
NH 2OH
Methylamine 4.4 × 10–4
CH 3 NH 2
Pyridine 1.7 × 10–9
C5 H 5 N
In solving problems involving weak bases, you should follow the same guidelines as you
followed for weak acids. The main difference is that we calculate OH −  first, instead of
 H + 
Example 1.7
What is the hydronium-ion concentration of a 0.20 M solution of ammonia in water?
Kb = 1.8 × 10–5
Solution: NH 3 (aq ) + H 2O(l )  NH 4 + (aq ) + OH − (aq )
initial conc. 0.20 M ----- -----
changes −x +x +x
equlib.conc. 0.20M-x x x
 NH 4 +  OH − 
The equilibrium equation for the reaction is given by: Kb =
NH 3
Substituting the concentration of NH 3 , NH 4 + and OH − in terms of x, gives:
( x)( x)
Kb =
(0.20 − x)
−5x2
1.8 x 10 =
0.20 − x
Since NH 3 is a weak base, and weak bases ionize only to a slight extent, x
must be small compared to 0.20. Therefore, you can make the approximation:
0.20 − x ≈ 0.20
x = 3.6 x 10−6 = 1.897 x 10−3

Now, the equation becomes (1.8 x 10−5 )(0.20) = x 2
27
CHEMISTRY GRADE 12
Exercise 1.8
1. For a 0.040 M ammonia solution:
a. Write a chemical equation that shows the ionization of ammonia in water.
b. Calculate the equilibrium concentration of ammonia, ammonium ions
and hydroxide ions, using the approximation method. Check whether the
approximation is valid or not.
c. If the approximation is invalid, use the quadratic formula to calculate the
concentration of ammonia, ammonium ions and hydroxide ions.
d. Calculate the pOH and pH of the solution.
1.3 COMMON ION EFFECT AND BUFFER SOLUTION

 define the common-ion effect;
 explain the importance of the common-ion effect;
 define buffer solution;
 give some common examples of buffer systems;
 explain the action of buffer solutions and its importance in chemical
processes;
 calculate the pH of a given buffer solution; and
 demonstrate the buffer action of CH 3COOH / CH 3COONa
1.3.1 The Common ion Effect
Activity 1.7
In Grade 11 Chemistry, you learned Le Chatelier’s principle. Make a group and

discuss the following and present your report to the class. Industrially, ammonia
is produced by the Haber process.
1. Write a chemical equation for the production of ammonia in the process.
2. Assume that the reaction is at equilibrium. What is the effect of
a. adding more ammonia to the equilibrium system?
b. removing ammonia from the equilibrium system?
c. adding more hydrogen gas to the equilibrium system?
d. decreasing the concentration of both hydrogen and nitrogen gases from
the equilibrium system?
28
e. increasing temperature?
f. decreasing pressure?
g. adding finely divided iron as a catalyst?
The common-ion effect is the shift in an ionic equilibrium caused by the addition of a
solute that provides an ion that takes part in the equilibrium. The common-ion effect occurs
when a given ion is added to an equilibrium mixture that already contains that ion. It is the
shift in an ionic equilibrium caused by the addition of a solute that provides an ion that
takes part in the equilibrium.
Consider a solution of acetic acid, CH 3COOH , in which you have the following acid-
ionization equilibrium:
CH 3COOH (aq ) + H 2O(l )  CH 3COO − (aq ) + H 3O + (aq )
Suppose you add HCl (aq) to this solution. What is the effect on the acid-ionization
equilibrium?
Because HCl (aq) is a strong acid, it provides H 3O + ion, which is present on the right
side of the equation for acetic acid ionization. According to LeChâtelier’s principle, the
equilibrium composition should shift to the left
CH 3COOH (aq ) + H 2O(l ) ← CH 3COO − (aq ) + H 3O + (aq )

added
The degree of ionization of acetic acid is decreased by the addition of a strong acid. This
repression of the ionization of acetic acid by HCl (aq) is an example of the common-ion
effect. Another example is, if sodium acetate and acetic acid are dissolved in the same
solution, they both dissociate and ionize to produce CH 3COO − ions, we can represent the
effect of acetate salts on the acetic acid equilibrium as:
29
CHEMISTRY GRADE 12
Example 1.8
Determine the  H 3O +  and CH 3COO −  in a solution that is 0.10 M in both
CH 3COOH and HCl .
Solution:
0.10 M HCl ionizes completely to form 0.10 M H 3O + and 0.10 M Cl − ions.
The Cl − ion is a spectator ion, and it has no influence on the concentrations of
CH 3COO − and H 3O +
CH 3COOH (aq ) + H 2O(l )  CH 3COO − (aq ) + H 3O + (aq )
initial conc. 0.10 M ----- 0.10 M
changes −x +x +x
equlib.conc. 0.10 M − x x 0.10 M + x
 H 3O +  CH 3COO −  (0.1 + x)( x)
=Ka =
[CH 3COOH ] (0.1 − x)
(0.10 + x)( x)
1.8 x 10−5 =
(0.10 − x)
If x is very small, you can approximate (1.00 –x) and (1.00 +x) to 1.00
(0.10)( x)
1.8 x 10−5 =
(0.10)
=x =
CH 3COO −  1.8 x 10−5 M
 H 3O +  =+
0.10 1.8 x 10−5 =
1.9 x 10−5 M
30
Exercise 1.9
a. Calculate the pH of a solution containing 0.20 M CH 3COOH and 0.30 M
CH 3COONa
b. What would be the pH of a 0.20 M CH 3COOH solution if no salt were

present?
1.3.2 Buffer Solutions
How does a buffer solution resist a pH change?
A buffer is commonly defined as a solution that resists changes in pH when a small amount
of acid or base is added or when the solution is diluted with pure solvent. This property
is extremely useful in maintaining the pH of a chemical system at an optimum value to
appropriately influence the reaction kinetics or equilibrium processes. A buffer solution
actually is a mixture of a weak acid and its conjugate base or a mixture of a weak base and
its conjugate acid. The conjugate forms are commonly referred to as “salts”.
Table1.4: Comparison of buffered and un buffered solutions.
Initial pH of pH after addition pH after addition

1.0 L sample of 0.010 mol NaOH of 0.010 mol HCl
Un buffered solution:1.28 × 4.8 12.0 2.0
10–5 M HCl
Buffered solution:0.099M 4.8 4.8 4.7
CH 3COOH
0.097M CH 3COONa
A buffer solution must contain a relatively large concentration of acid to react with any
OH − ions that may be added to it. Similarly, it must contain a large concentration of base to
react with any added H + ions. Furthermore, the acid and the base components of the buffer
must not consume each other in a neutralization reaction. These requirements are satisfied
by an acid-base conjugate pair (a weak acid and its conjugate base or a weak base and its
conjugate acid).
A simple buffer solution can be prepared by adding comparable amounts of acetic acid (
CH 3COOH ) and sodium acetate ( CH 3COONa ) to water. The equilibrium concentrations
31
CHEMISTRY GRADE 12
of both the acid and the conjugate base (from CH 3COONa ) are assumed to be the same as
the starting concentrations. This is so because
−
1. CH 3COOH is a weak acid and the extent of hydrolysis of the CH 3COO ion is very
small and
2. the presence of CH 3COO − ions suppress the ionization of CH 3COOH , and the
presence of CH 3COOH suppresses the hydrolysis of the CH 3COO − ions
A solution containing these two substances has the ability to neutralize either added acid or
added base. Sodium acetate, a strong electrolyte, dissociates completely in water:
H O
2 → CH COO − ( aq ) + Na + ( aq )
CH 3COONa ( s )  3
If an acid is added, the H + ions will be consumed by the conjugate base in the buffer,
CH 3COO − ,according to the equation
CH 3COO − (aq ) + H + (aq ) → CH 3COOH (aq )
If a base is added to the buffer system, the OH − ions will be neutralized by the acid in the
buffer:
CH 3COOH (aq ) +OH − (aq ) → CH 3COO − (aq ) + H 2O(l )
Thus, a buffer solution resists changes in pH through its ability to combine with the H + and
OH − ions.
Buffers are very important to chemical and biological systems. The pH in the human
body varies greatly from one fluid to another; for example, the pH of blood is about 7.4,
whereas the gastric juice in our stomachs has a pH of about 1.5. These pH values, which
are crucial for the proper functioning of enzymes and the balance of osmotic pressure, are
maintained by buffers in most cases. The pH of a buffer solution can be estimated with
the help of Henderson–Hasselbalch equation when the concentration of the acid and its
conjugate base, or the base and the corresponding conjugate acid, are known.
The Henderson-Hasselbach equation is derived from the definition of the acid dissociation
constant as follows.
32
Consider the hypothetical compound HA in water. The dissociation equation and K a ex-
pression are
HA + H 2O  H 3O + + A−
 H 3O +   A− 
Ka =
[ HA]
The key variable that determines [ H 3O + ] is the concentration ratio of acid species to base
species, so, rearranging to isolate [ H 3O + ] gives
 H 3O +  = K a x
[ HA]
 A− 
Taking the negative logarithm of both sides gives
 [ HA] 
− log K a − log  − 
− log  H 3O +  =
 A  
 
 [ HA] 
pH pK a − log  − 
from which definitions gives =
 A  
Rearranging the equation gives  
  A−  
pH pK a + log    
=
 [ HA] 
 
Generalizing the previous equation for any conjugate acid-base pair gives the Henderson-
Hasselbalch equation:
 [Conjugate base] 
=
pH pK a + log 
 [ weak acid ] 
 
Similarly, for a weak base dissociation:
 [Conjugate acid ] 
= pK b + log 
 [ weak base] 
pOH
 
33
CHEMISTRY GRADE 12
Example 1.9
1. What is the pH of a buffer solution consisting of 0.035 M NH 3 and 0.050
M NH 4 + (Ka for NH4+ is 5.6 x 10-10)? The equation for the reaction is:
NH 4 +  H + + NH 3
Assuming that the change in concentrations is negligible in order for the system
to reach equilibrium, the Henderson-Hasselbalch equation will be:
 [ NH ] 
pH pK a + log 
= 3

  NH 4 +  
 
 0.035 
= 9.23 + log 
pH 
 0.050 
pH = 9.095
2. A buffer is made by mixing 0.060 M NH 3 with 0.040 M NH4Cl. What is the
pH of this buffer? K b = 1.8 x 10−5
Solution
The buffer contains a base and its conjugate acid in equilibrium. The equation is
NH 3 (aq ) + H 2O(l )  NH 4 + (aq ) + OH − (aq )
Assuming that the change in concentrations is negligible in order for the system
to reach equilibrium,
the Henderson-Hasselbalch equation will be:
 [Conjugate acid ] 
= pK b + log 
 [ weak base] 
pOH
 
 NH 4 + 
= pK b + log 
pOH 
 NH 3 
 0.04 
= 4.745 + log 
pOH 
 0.06 
= 4.745 − 0.1761
pOH
= 4.5689
pH= 14 − pOH
= 14 − 4.5689
= 9.4311
34
Exercise 1.10
1. Calculate the pH :
a. of a buffer solution containing 0.1 M CH 3COOH and a 0.1 M solution
of CH 3COONa .
b. when 1.0 mL of 0.10 M HCl is added to 100 mL of the buffer in (a);
c. when 1.0 mL of 0.10 M NaOH is added to 100 mL of the buffer in (a);
d. of an unbuffered solution containing 1.8 × 10 –5 HCl ;
e. change of an unbuffered solution in (d) after adding
2. i. 1.0 mL of 0.1 M NaOH to 100 mL of the solution,
ii.1.0 mL of 0.10 M HCl to 100 mL of the solution.
1.4 Hydrolsis of Salts

 define hydrolysis;
 explain why a salt of weak acid and strong base gives a basic solution;
 explain why a salt of strong acid and weak base gives an acidic solution;
and
 explain why salts of weak acids and weak bases give acidic, basic or
neutral solutions.
What does salt hydrolysis mean?
Hydrolysis is a common form of a chemical reaction where water is mostly used to break
down the chemical bonds that exist between particular substances. Hydrolysis is derived
from a Greek word hydro meaning water and lysis meaning break or to unbind. Usually
in hydrolysis the water molecules get attached to two parts of a molecule. One molecule
of a substance will get H + ion and the other molecule receives the OH − group. The term
salt hydrolysis describes the “interaction of anion and cation of a salt, or both, with water.
Depending on the strengths of the parent acids and bases, the cation of a salt can serves as
an acid, base or neutral.
1.4.1 Hydrolysis of Salts of Strong Acids and Strong Bases
The reaction between a strong acid (say, HCl ) and a strong base (say, NaOH ) can be
represented by NaOH (aq ) + HCl (l ) → NaCl (aq ) + H 2O(l )
or in terms of the net ionic equation
35
CHEMISTRY GRADE 12
H + (aq ) + OH − (aq ) → H 2O(l )
The anions derived from strong acids are weak conjugate bases and do not undergo
hydrolysis. The cations derived from strong bases are weak conjugate acids and also do
not hydrolysis. The strong bases are the ionic hydroxides of Group IA and IIA metals.
The cations of these metals also do not hydrolyze. It involves only ionization of water and
no hydrolysis..For the above reaction, chloride ions, Cl− , and sodium ions, Na + , do not
hydrolyze, the solution of the salt will be neutral ( pH =7).
Can you give more examples?
1.4.2 Hydrolysis of Salts of weak acids and strong bases
Consider the neutralization reaction between acetic acid (a weak acid) and sodium
hydroxide (a strong base):
CH 3COOH (aq ) + NaOH (aq ) → CH 3COONa(aq)+H 2O(aq )

This equation can be simplified to
CH 3COOH (aq ) + OH − (aq ) → CH 3COO − (aq)+H 2O(aq )

The acetate ion undergoes hydrolysis as follows:
CH 3COO − (aq)+H 2O(aq ) → CH 3COOH (aq ) + OH − (aq )

Therefore, at the equivalence point, when we only have sodium acetate present, the pH
will be greater than7 as a result of the excess OH − ions formed. Note that this situation is
analogous to the hydrolysis of sodium acetate ( CH 3COONa )Therefore, solutions of these

salts are basic because the anion of the weak acid is a moderately strong base and can be
hydrolyzed.
Activity 1.8
Consider NaNO2 and discuss the following:
a. What are the ‘parents’ (acid and base) of this salt?
b. Which ions of the salt can be hydrolyzed?
c. What will be the nature of NaNO2 solution? Will it be acidic, basic or
neutral?
36
1.4.3 Hydrolysis of Salts of strong acids and weak bases
When we neutralize a weak base with a strong acid, the product is a salt containing the
conjugate acid of the weak base. This conjugate acid is a strong acid. For example, ammo-
nium chloride, NH 4 Cl , is a salt formed by the reaction of the weak base ammonia with the
strong acid HCl :
NH 3 (aq)+HCl (aq ) → NH 4Cl (aq )
A solution of this salt contains ammonium ions and chloride ions. Chloride is a very
weak base and will not accept a proton to a measurable extent. However, the ammonium
ion, the conjugate acid of ammonia, reacts with water and increases the hydronium ion
concentration:
NH 4 + (aq ) +H 2 O(l) → H 3O + (aq ) + NH 3 (aq)
1.4.4 Hydrolysis of Salts of weak acids and week bases
Solutions of a salt formed by the reaction of a weak acid and a weak base involve both
cationic and anionic hydrolysis. To predict whether the solution is acidic or basic you need
to compare the K a of the weak acid and the K b of the weak base. If the K a is larger than the
K b , the solution is acidic, and if the K a is less than the K b , the solution is basic. If they are
equal the solution is neutral. Consider solutions of ammonium formate, NH 4CHO2 . These
solutions are slightly acidic, because the K b for NH 4 + ( 5.6x 10-10) is somewhat larger than
the K b for formate ion, CHO2 − ( 5.9 x 10-11).
37
CHEMISTRY GRADE 12
Activity 1.9
In the following table you are given K a and K b values of some cations and
anions, respectively.
Anion Kb Cation Ka
F− 1.4 × 10–11 NH 4 + 5.6 × 10–10
CNS − 2.0 × 10–5 5.6 × 10–10
CH 3COO −
Using the above table, determine whether the solutions of NH 4 F , NH 4 CNS

and CH 3COONH 4 are acidic, basic or neutral. Discuss your results with your
classmates.
1.5 Acid–Base Indicators and Titrations

 define acid-base indicators;
 write some examples of acid-base indicators;
 suggest a suitable indicator for a given acid-base titration;
 explain the equivalents of acids and bases;
 calculate the normality of a given acidic or basic solution;
 define acid-base titration;
 distinguish between end point and equivalent point; and
 discuss the different types of titration curves
1.5.1 Acid–Base Indicators
How do acid-base indicators change color?
Acid-base indicators are weak organic acids (denoted here as HIn ) or weak organic bases
( In − ) that indicate whether a solution is acidic, basic or neutral. The color of the indicator
depends on the pH of the solution to which it is added. When just a small amount of
indicator is added to a solution, the indicator does not affect the pH of the solution.
Instead, the ionization equilibrium of the indicator is affected by the prevailing  H 3O +  in

the solution
38
HIn + H 2O  H 3O + + In −
Acid colour Ba se c olour
If the indicator is in a sufficiently acidic medium [increasing  H 3O +  ], the equilibrium,

according to Le Châtelier’s principle, shifts to the left and the predominant color of the
indicator is that of the non-ionized form ( HIn ). On the other hand, in a basic medium
[Decreasing  H 3O +  ] the equilibrium shifts to the right and the color of the solution will be
due mainly to that of the conjugate base ( In − ).
An acid–base indicator is usually prepared as a solution (in water, ethanol, or some other
solvent). In acid–base titrations, a few drops of the indicator solution are added to the
solution being titrated. In other applications, porous paper is impregnated with an indicator
solution and dried. When this paper is moistened with the solution being tested, it acquires
a color determined by the pH of the solution. This paper is usually called pH test paper.
Table 1.5: Some common indicators.
Indicator change Acid Color Base Color pH range of Color

Methyl violet Yellow Violet 0.0 – 1.6
Methyl orange Red Yellow 3.2 – 4.4
Bromcresol green Yellow Blue 3.8 – 5.4
Methyl red Red Yellow 4.8 – 6.0
Litmus Red Blue 5.0 – 8.0
Phenolphthalein Colorless Pink 8.2 – 10.0
Example 1.10
What is the pH of a buffer prepared with 0.40 M CH 3COOH and 0.20 M
CH 3COO − if the K a of CH 3COOH is 1.8 x 10 -5 ? Which type of indicator is used
to check the acidity or basicity of this solution?
=  H 3O +  K=
[CH 3COOH ] 1.8 x 10−5 M x 0.40
a x
CH 3COO −  0.20
Solution:
 H 3O +  = 3.6 x 10−5 M
− log(3.6 x 10−5 ) =
pH = 4.44
The pH value indicates that the solution is acidic
39
CHEMISTRY GRADE 12
1.5.2 Equivalents of Acids and Bases
The reactive capacity of a chemical species, the ions or electrons, depends on what is being
transferred in a chemical reaction. In acid-base reactions, an equivalent is the amount of
a substance that will react with one mole of hydrogen ions. For acids, an equivalent is
the number of hydrogen ions a molecule transfer. For example, for Sulfuric acid ( H 2 SO4 )
equivalents is equal to 2.
For bases, it is the number of hydroxide ions ( OH − )ions provided for a reaction, for
example for Barium hydroxide ( Ba (OH ) 2 )equivalents is equal to 2.
The normality of a solution refers to the number of equivalents of solute per Liter of solu-
tion.
Number of equivalents of solutes

Normality =
Liters of solution
The definition of chemical equivalent depends on the substance or type of chemical re-
action under consideration. Because the concept of equivalents is based on the reacting
power of an element or compound, it follows that a specific number of equivalents of one
substance will react with the same number of equivalents of another substance. When the
concept of equivalents is taken into consideration, it is less likely that chemicals will be
wasted as excess amounts. Keeping in mind that normality is a measure of the reacting
power of a solution, we use the following equation to determine normality:
Thus, according to the definition of normality, the number of equivalents is the normality
multiplied by the volume of solution, in litters. If we add enough acid to neutralize a given
volume of base, the following equation holds:
N1V1 = N 2V2
Where N1and V1refer to the normality and volume of the acid solution, respectively, and N2
and V2 refer to the normality and volume of the base solution, respectively.
40
Example 1.11
What volume of 2.0 N NaOH is required to neutralize 25.0 mL of 2.70 N H 2 SO4
?
Solution:
N1V1 = N 2V2
N1V1
V2 =
N2
(2.7 N H 2 SO4 )(25.0 mL H 2 SO4 )

V2 NaOH =
2.0 N NaOH
= 33.8 mL
1.5.3 Acid–Base Titrations
An acid–base titration is a procedure for determining the amount of acid (or base) in a
solution by determining the volume of base (or acid) of known concentration that will
completely react with it. In a titration, one of the solutions to be neutralized say, the acid
is placed in a flask or beaker, together with a few drops of an acid base indicator (Figure
1.2). The other solution (the base) used in a titration is added from a burette and is called
the titrant. The titrant is added to the acid (Titrand or analyte), first rapidly and then drop by
drop, up to the equivalence point. The equivalence point of the titration is the point at which
the amount of titrant added is just enough to completely neutralize the analyte solution. At
the equivalence point in an acid-base titration, moles of base are equal to moles of acid and
the solution contains only salt and water. The equivalence point is located by noting the
color change of the acid base indicator. The point in a titration at which the indicator changes
color is called the end point of the indicator. The end point must match the equivalence
point of the neutralization. That is, if the indicators end point is near the equivalence point
of the neutralization, the color change marked by that end point will signal the attainment
of the equivalence point. This match can be achieved by use of an indicator whose color
change occurs over a pH range that includes the pH of the equivalence point. Knowing
the volume of titrant added allows the determination of the concentration of the unknown
analyte using the following relation
volume of base x concentration of base = volume of acid x unknown concentration of acid
volume of base x concentration of base

unknown concentration of acid =
volume of acid
41
CHEMISTRY GRADE 12
Figure 1.2: The Techniques of Titration.
An acid–base titration curve is a plot of the pH of a solution of acid (or base) against
the volume of added base (or acid). Such curves are used to gain insight into the titration
process.
Experiment 1.1
Acid-base Titration
Objective: To find the normality of a given hydrochloric acid solution by titrating

against 0.1 N standard sodium hydroxide solution.
Apparatus: 10 mL pipette, burette, 150 mL Erlenmeyer flask, beaker, funnel, bu-

rette clamp and metal stand.
Procedure:
1. Clean the burette with distilled water and rinse it with the 0.1 N sodium hydrox-
ide solution; and fix the burette on the burette clamp in vertical position (Figure
1.3).
2. Using a funnel, introduce 0.1 N sodium hydroxide solutions into the burette. Al-
low some of the solution to flow out and make sure that there are no air bubbles
in the solution (why?).
3. Record level of the solution, corresponding to the bottom of the meniscus, to the
nearest 0.1 mL.
42
4. Measure exactly 10 mL of hydrochloric acid solution (given) with the help of

a10 mL pipette and add it into a clean 150 mL Erlenmeyer flask and add two or
three drops of phenolphthalein indicator.
5. Caution: When you suck hydrochloric acid or any reagent solution, into a pi-
pette, have the maximum caution not to suck it into your mouth.
6. Titration: First hold the neck of the Erlenmeyer flask with one hand and the
stopcock with the other. As you add the sodium hydroxide solution from the
burette, swirl the content of the flask gently and continuously.
7. Add sodium hydroxide solution until the first faint pink color comes which dis-
appears on swirling.
8. Add more sodium hydroxide drop wise until the pink color persists for a few
seconds.
9. Find the difference between the initial level and the end point level of the bu-
rette.
Observations and analysis:
1. Color change at the end point is from __________ to _________.

2. What is the volume of sodium hydroxide added at the end point?
3. What is the normality of hydrochloric acid at the end point?
4. What is the similarity and difference between equivalence point and end point
level after reaching the end point?
Figure 1.3: Titration Setup.
43
CHEMISTRY GRADE 12
Unit Summary
~ By the Arrhenius definition, an Arrhenius acid produces H + and an Arrhenius
base produces OH − in aqueous solutions. And an acid-base reaction (neutral-
ization)is the reaction of H + and OH − to form H 2O .The Arrhenius definition
of acids and bases has many limitations but still we cannot ignore it.
~ The Brønsted-Lowry acid-base definition does not require that bases contain
OH − in their formula or that acid-base reactions occur in aqueous solution.
An acid is a species that donates a proton and a base is one that accepts it, so
an acid-base reaction is a proton-transfer process. When an acid donates a pro-
ton, it becomes the conjugate base; when a base accepts a proton, it becomes
the conjugate acid. In an acid-base reaction, acids and bases form their conju-
gates. A stronger acid has a weaker conjugate base, and vice versa.
~ Brønsted-Lowry bases include NH 3 and amines and the anions of weak acids.
All produce basic solutions by accepting H + from water, which yields OH − ,
thus making  H 3O +  < OH − 
~ The Lewis acid-base definition focuses on the donation or acceptance of an
electron pair to form a new covalent bond in an addict, the product of an
acid-base reaction. Lewis bases donate the electron pair, and Lewis’s acids ac-
cept it. Thus, many species that do not contain H + act as Lewis’s acids; exam-
ples are molecules with electron-deficient atoms and those with polar double
bonds. Metal ions act as Lewis’s acids when they dissolve in water, which acts
as a Lewis base, to form the adduct, a hydrated cation
~ Pure water auto ionizes to a small extent in a process whose equilibrium con-
stant is the ion product constant for water, K w (1.0 x 10-14 at 25 0C).  H 3O + 
and OH −  are inversely related: in acidic solution,  H 3O +  is greater than
OH −  ; the reverse is true in basic solution; and the two are equal in neu-
tral solution. To express small values of  H 3O +  , we use the pH scale (
pH = − log  H 3O +  ). Similarly, pOH = − log OH −  and. pK = − log K
~ A high pH represents a low  H 3O +  . In acidic solutions, pH < 7; in basic
solutions, pH > 7; and in neutral solutions pH = 7. The sum of pH and pOH
equals pK w (14.00 at 25 0C).
~ Acid strength depends on  H 3O +  relative to [ HA] in aqueous solution.
Strong acids dissociate completely and weak acids slightly.
~ The extent of dissociation is expressed by the acid-dissociation constant, K a .
Most weak acids have K a values ranging from about 10-2 to 10-10.
~ The pH of a buffered solution changes much less than the pH of an unbuff-
ered solution when  H 3O +  or OH − is added.
44
~ An acid-base reaction proceeds to the greater extentin the direction in which a

stronger acid and base form a weaker base and acid.
~ Two common types of weak-acid equilibrium problems involve finding K a
from a given concentration and finding a concentration from a given K a .
~ The extent to which a weak base accepts a proton from water to form OH − is
expressed by a base-dissociation constant, K b .
~ By multiplying the expressions for K a of HA and K b of A− , we obtain K w .
This relationship allows us to calculate either K a of BH + or K b of A− .
~ A buffer consists of a weak acid and its conjugate base (or a weak base and its
conjugate acid).To be effective, the amounts of the components must be much
greater than the amount of  H 3O +  or OH − added.
~ The buffer-component concentration ratio determines the pH ;the ratio and the
pH are related by the Henderson-Hasselbalch equation.
~ When  H 3O +  or OH − is added to abuffer, one component reacts to form the
other; thus  H 3O +  (and pH ) changes only slightly.
~ A concentrated (higher capacity) buffer undergoes smaller changes in pH than
a dilute buffer. When the buffer pH equals the pK a of the acid component, the
buffer has its highest capacity.
Check List
Key terms of the unit
 Arrhenius acid-base concept

 Bronsted-Lowry concept of acid and bases
 Conjugate acid and Conjugate base
 Lewis’s concept of acids and bases
 Autoionization
 Amphiprotic species
 pH scale
 percent ionization
 Hydrolysis of salts
 Buffer solution
 Common ion effect
 Equivalents of acids and bases
 Acid-base titration
45
CHEMISTRY GRADE 12
REVIEW EXERCISE FOR UNIT 1

Part I Multiple Choice
1. Which of the following is a Brønsted-Lowry base but an Arrhenius base?
a. NH3 b. NaOH c. Ca (OH)2 d. KOH
2. Use the following acid ionization constants to identify the correct decreasing order of
base strengths.
HF Ka = 7.2 x 10–4HNO2 Ka = 4.5 x 10–4 HCN Ka = 6.2 x 10–10
a. CN–>NO2–> F– b. F–>NO2–>CN– c. NO2–> F–> CN– d. NO2–> CN–>F–
3. In the Brønsted–Lowry definition of acids and bases, an acid __________
a. is a proton donor. b. breaks stable hydrogen bonds.
c. is a proton acceptor. d. corrodes metals.
4. Which of the following is the conjugate acid of the hydrogen phosphate ion, HPO42–?
a. H3PO4 b. PO43– c. H2PO4– d. H3O+
5. Which one of the following is not a conjugate acid–base pair?
a. NH3 and NH4+ b. HS– and H2S c. NH3 and NH2– d. H3O+ and OH–
6. Which one of the following is not a conjugate acid–base pair?
a. NH3 and NH2– b. H2PO4– and HPO42– c. HNO3 and HNO2 d. H2O and OH–
7. Which one of the following is not a strong acid?
a. nitric acid, HNO3 b. carbonic acid, H2CO3
c. sulfuric acid, H2SO4 d. perchloric acid, HClO4
8. Each of the following pairs contains one strong acid and one weak acid EXCEPT:
a. H2SO4 and H2CO3 b. HNO3 and HNO2
c. HBr and H3PO2 d. HSO4─ and HCN
9. When [H+] = 4.0 × 10–9 M in water at 25°C, then __________
a. pH = 9.40. b. pH = 8.40. c. pH = 7.00. d. pH = –9.40
10. A solution with an [OH–] concentration of 1.20 × 10–7 M has a pOH and pH of
__________
a. 6.92 and 7.08 b. 7.08 and 6.92 c. 1.00 and 13.00 d. 5.94 and 8.06
46
11. The acidic ingredient in vinegar is acetic acid. The pH of vinegar is around 2.4, and
the molar concentration of acetic acid in vinegar is around 0.85 M. Based on this
information, determine the value of the acid ionization constant, Ka, for acetic acid.
a. 2.5 × 10–5 b. 1.9 × 10–5 c. 5.0 × 10–5 d. 7.4 × 10–3
12. A cup of coffee has a hydroxide ion concentration of 1.0 × 10–10 M. What is the pH of
this coffee?
a. 6 b. 7 c. 4 d. 2
13. What is the concentration of [OH–] in a 0.20 M solution of ammonia? The Kb value for
ammonia is 1.8 × 10–5 .
a. 3.6 × 10–6 M b. 1.8 × 10–5 M c. 1.9 × 10–3 M d. 4.2 × 10–4 M
14. Whcih of the following molecules is not a lewis base?
a. HCl b NH3 c. BH3 d. NaOH
15. Which one of the following salts forms aqueous solutions with pH = 7?
a. Na2S b. NaNO2 c. NaBr d. Na2CO3
Part II: Short Answer Questions

1. Define acids and bases based on the concept of
a. Arrhenius b. Brønsted-Lowry c. Lewis
2. In each of the following equations, identify the reactant that is a Brønsted–Lowry

acid and the reactant that is a Brønsted–Lowry base:
HBr (aq ) + H 2O(l ) → H 3O + (aq ) + Br − (aq )

a.
− −
b. CN (aq) + H 2O(l )  HCN(aq) + OH (aq)
3. Identify the Bronsted -Lowery acid - base pairs in each of the following equations.
− +
a. H 3 PO (aq) + H 2O(l )  H 2 PO4 (aq ) + H 3O (aq )
b. CO32− (aq ) + H 2O(l )  HCO3− (aq ) + OH − (aq )
c. H 3 PO (aq) + NH 3 (aq)  H 2 PO4 − (aq) + NH 4 + (aq)

4
4. According to the Lewis theory, each of the following is an acid base reaction. Which
species is the acid and which is the base?
a. BF3 + F − → BF4 − b. OH − (aq ) + CO2 (aq ) → HCO3− (aq )
47
CHEMISTRY GRADE 12
5. Classify each of the following compounds as a strong acid, weak acid, strong base, or
weak base:
a. KOH b. (CH3)2CHCOOH c.H2SeO4 d. (CH3)2CHNH2
6. Which of the following are amphiprotic?

a. OH─ b. NH3 c. H2O d. H2S e. NO3– f. HCO3– g.CH3COO– h. HNO3
7. A research chemist adds a measured amount of HCl gas to pure water at 25 0C and
obtains a solution with [H3O+] = 5 3.0 x 10-4M. Calculate [OH─]. Is the solution
neutral, acidic, or basic?
8. Calculate the percent ionization of a 0.125 M solution of nitrous acid (a weak acid),
with a pH of 2.09
9. A vinegar solution has a [OH-] = 5.0 x 10-12 M at 25 °C. What is the [H3O+] of the
vinegar solution? Is the solution acidic, basic, or neutral?
10. The Ka for acetic acid, HC2H3O2, is 1.8 x 10-5. What is the pH of a buffer prepared
with 1.0 M HC2H3O2 and 1.0 M C2H3O2- ?
HC2 H 3 O2 (aq) + H 2O(aq )  H 3O + (aq) + C2 H 3O 2 − (aq)
48
Electro chemistry
UNIT
ELECTRO CHEMISTRY
2
Unit Outcomes
After completing this unit, students will be able to:

 describe the fundamental concepts related to oxidation- reduction
reaction;
 explain the application of redox reactions in production of new
substances and energy;
 demonstrate an understanding of fundamental concepts related to the
interconversion of chemical & electrical energy;
 distinguish between metallic conduction & electrolytic conduction;
 identify & describe the functioning of the components of electrolytic &
galvanic cells;
 distinguish difference between electrolytic & galvanic cells;
 apply Faradays laws to solve problems associated with electrolysis
experiment;
 measure through experimentation the mass of metal deposited by
electroplating (e.g.:- copper from copper(II) sulphate), & apply
Faraday’s law to relate the mass of metal deposited to the amount of
charge passed;
 predict the spontaneity of redox reactions & overall cell potentials by
studying a table of half-cell reduction potentials;
 determine the emf of an electrochemical cell experimentally or from
given data;
 explain the application of electrochemistry in our daily lives & in
industry;
49
CHEMISTRY GRADE 12
 explain corrosion as an electrochemical process, & describe

corrosion- inhibiting techniques (e.g., painting, galvanizing, cathodic
protection);
 describe examples of common galvanic cells & evaluate their
environmental & social impact;
 Demonstrate scientific enquiry skills along this unit: observing,
classifying, comparing & contrasting, communicating, asking question,
measuring, relating cause & effect and problem solving.
2.1 OXIDATION-REDUCTION REACTIONS
After completing this subunit, you will be able to:

 define redox reaction
 define oxidation in terms of electron transfer and change in oxidation
number.
 define reduction in terms of electron transfer and change in oxidation
number.
 describe the oxidizing and reducing agents
 identify the species that are oxidized and reduced in a given redox
reaction and determine the oxidizing and reducing agents
Startup Activity
Form a group and discuss the following questions,
4. What are oxidation-reduction (redox) reactions?
5. List the redox-reactions taking place in your body, and the surroundings.
After discussion, share your idea with other groups.
2.1.1 Oxidation
When do we say a substance is oxidized?
The term oxidation was originally defined in terms of the adding of oxygen to a compound.
However, nowa days it has a broader meaning that includes reactions involving not only
oxygen. In this case Oxidation is a process in which an atom/element loses an electron and
therefore increases its oxidation number.
50
Electro chemistry
2.1.2 Reduction
When do we say a substance is reduced? Can oxidation occur without reduction and vice
versa?
The term reduction was originally used to describe the production of a metal from an ore. It
has been modified through time to include other reactions. Thus, Reduction is a process in
which an atom gains an electron and therefore decreases its oxidation number.
Consider the following example
0 1+ 2+ 0
Mg ( s ) + 2 H Cl ( aq ) → Cl
Mg 2 ( aq ) + H (g)
In the above reaction Mg metal is oxidized and H+ ions are reduced; the Cl- ions are spectator
ions. Note that oxidation and reduction reactions are always occur in pairs. Since oxidation
and reduction reactions cannot occur independently, they as a whole are called ‘Redox
Reactions’.
Activity 2.1
Form a group and discuss the following questions and present your answers to
the class.
1. Which of the following reactions are redox reactions? Explain your answer
for each case.
a. Ca ( s ) + 2 H 2O(l ) → Ca (OH ) 2 (aq ) + H 2 ( g )
b. H 2 SO4 (aq ) + 2 NaOH (aq ) → Na2 SO4 (aq ) + 2 H 2O (l )
c. AgNO3 (aq ) + NaCl (aq ) → AgCl ( s ) + NaNO3 (aq )
2. Use the given chemical equation to answer the following questions;
Mg ( s ) + Zn 2+ (aq ) → Zn( s ) + Mg 2+ (aq )
Identify the:
a. oxidized substance b. reduced substance.
c. oxidizing agent. d. reducing agent.
Calculate the oxidation number of:
a. C in C2O4 2−
b. Cr in K 2CrO4
c. Cl in HClO4
51
CHEMISTRY GRADE 12
2.1.3 Balancing Oxidation-Reduction (Redox) Reactions
What scientific law is used in balancing chemical equations?
Because atoms are neither created nor destroyed in an ordinary chemical reaction, chemical
equations must have an equal number of atoms of each element on the reactant and product
sides. In addition, the net electrical charges in the reactant side must be equal to the net
electrical charges in the product side. The methods used to balance redox reactions are the
change in oxidation number methods and Half-reaction methods.
Balancing Redox Reactions Using Change in Oxidation-Number Method

How do you balance redox reactions using the change in the oxidation-number method?
This method is used to balance redox reactions that do not occur in aqueous solutions, and
also reactions that do not involve ions. Steps used to balance the chemical equations using
the change in oxidation state method are:
1. Write an unbalanced chemical equation

2. Assign oxidation numbers to all elements in the reaction
3. From the changes in oxidation numbers, identify the oxidized and reduced species
4. Compute the number of electrons lost in the oxidation and gained in the reduction
from the oxidation number s changes
5. Multiply one or both of these numbers by appropriate factors to make the electrons
lost equal the electrons gained, and use the factors as balancing coefficients
6. Complete the balancing by inspection, adding states of matter
Example 2.1
1. Balance the following chemical equation, using the change in oxidation-
number method.
PbS ( s ) + O2 ( g ) → PbO( s ) + SO2 ( g )

Solution
Step 1. Write an unbalanced chemical equation
PbS ( s ) + O2 ( g ) → PbO( s ) + SO2 ( g )

Step 2Assign oxidation numbers to all elements
+2 −2 0 +2 −2 +4 −2
Pb S ( s ) + O2 ( g ) → Pb O( s ) + S O2 ( g )
52
Electro chemistry
Step 3. Identify oxidized and reduced species

– PbS was oxidized (Oxidation number of S changes from -2 to +4)
– O2 was reduced (Oxidation number of S changes from 0 to -2)
Step 4. Compute electron lost and electron gained
– In the oxidation: 6electronwere lost from S
– In the reduction: 2electron were gained by each O
Step 5. Multiply by factors to make electron lost equal to electron gained, and
use the factors as coefficients
S lost 6 electrons; O gained 4electrons (2 electron each O).
3
Thus, put the coefficient before O2
2
3
PbS ( s ) + O2 ( g ) → PbO( s ) + SO2 ( g )
2
Step 6. Complete the balancing by inspection
3
2 PbS ( s ) + O2 ( g ) → 2 PbO( s ) + SO2 ( g )
2
The chemical equation is balanced, because the number of atoms in the reactant
side is equal to the number of atoms in the product side. It can also be confirmed
that the net charge is zero on each side.
Exercise 2.1
1. Use the oxidation number method to balance the following equations and
then identify the oxidizing and reducing agents:
a. HNO3 + H 3 AsO3 (aq ) → NO( g ) + H 3 AsO4 (aq ) + H 2O(l )
b. KClOü + HBr → Br + H O + KCl
c H 2 S + HNO3 → S + NO + H 2O
Balancing Redox Reactions using Half-Reaction Method

Why do you balance chemical equations?
In half-reaction method, the overall reaction is divided into two half-reactions, one for
oxidation and one for reduction. The equations for the two half-reactions are balanced
separately and then added together to give the overall balanced equation. Steps used to
balance the chemical equations using the Half-Reaction method are:
1. Separate the equation into oxidation half-reaction and reduction half-reaction
2. Balance the atoms and charges in each half-reaction.
 Atoms are balanced in this order: atoms other than O and H, then O , then H .
53
CHEMISTRY GRADE 12
For reactions in an acidic medium, add H 2O to balance the O atoms and H + to

balance the H atoms.
 Charge is balanced by adding electrons ( e − ) to the left side in the reduction half-
reaction and to the right side in the oxidation half-reaction.
3. cessary, multiply one or both half-reactions by an integer so that the number of e −
gained in reduction is equal to the number of e − lost in oxidation
4. Add the balanced half-reactions, and include states of matter.
5. Check that the atoms and charges are balanced.
Example 2.2
1. Use the half-reaction method to balance the following equation:
Fe 2+ + Cr2O7 2− → Fe3+ + Cr 3+
Solution
Step 1: Separate the equation into two half-reactions
Oxidation: Fe 2+ → Fe3+
Reduction: Cr2O7 2− → Cr 3+
Step 2: Balance each half-reaction for number and type of atoms and charges. For
reactions in an acidic medium, add H 2O to balance the O atoms and
to balance the H atoms.
Oxidation half-reaction: The atoms are already balanced. To balance the
charge, we add an electron to the right-hand side of the arrow:
Fe 2+ → Fe3+ + e −
Note: In an oxidation half-reaction, electrons appear as a product; in a reduction
half reaction, electrons appear as a reactant.
Reduction half-reaction: Because the reaction takes place in an acidic medium,
we add seven H 2O molecules to the right-hand side of the arrow to balance the
O atoms:
Cr2O7 2− → 2Cr 3+ + 7 H 2O
To balance the H atoms, we add 14 H + ions on the left-hand side:
14 H + + Cr2O7 2− → 2Cr 3+ + 7 H 2O
There are now 12 positive charges on the left-hand side and only six positive
charges on the right-hand side. Therefore, we add six electrons on the left
14 H + + Cr2O7 2− + 6e − → 2Cr 3+ + 7 H 2O
54
Electro chemistry
Step 3: Add the two half-reactions together and balance the final equation by
inspection. The electrons on both sides must cancel. If the oxidation and
reduction half-reactions contain different numbers of electrons, we need
to multiply one or both half-reactions to equalize the number of electrons
Here we have only one electron for the oxidation half-reaction and six
electrons for the reduction half-reaction, so we need to multiply the
oxidation half-reaction by 6 and write
6( Fe 2+ → Fe3+ + e − )
14 H + + Cr2O7 2− + 6e − → 2Cr 3+ + 7 H 2O
6 Fe 2+ + 14 H + + Cr2O7 2− + 6e − → 6 Fe3+ + 2Cr 3+ + 7 H 2O + 6e −
The electrons on both sides cancel, and we are left with the balanced net ionic
equation:
6 Fe 2+ + 14 H + + Cr2O7 2− → 6 Fe3+ + 2Cr 3+ + 7 H 2O

Step 4: Verify that the equation contains the same type and numbers of atoms and
the same charges on both sides of the equation.
For reactions in a basic medium, we proceed through step 4 as if the reaction
were carried out in a acidic medium. Then, for every H + ion we add an equal
number of OH − ions to both sides of the equation. Where H + and OH − ions
appear on the same side of the equation, we combine the ions to give H 2O .
2. Write a balanced ionic equation using the half-reaction method to represent
the oxidation of iodide ion (I- ) by permanganate ion ( MnO4- ) in basic
solution to yield molecular iodine ( I 2 ) and manganese (IV) oxide ( MnO4-
). MnO4− + I − → MnO2 + I 2
Solution
Step 1: The two half-reactions are
Oxidation: I − → I 2
Reduction: MnO4− → MnO2
Step 2: We balance each half-reaction for number and type of atoms and charges.
Oxidation half-reaction: We first balance the I atoms:
2I − → I 2
To balance charges, we add two electrons to the right-hand side of the equation:
2 I − → I 2 +2e _
Reduction half-reaction: To balance the O atoms, we add two H 2O molecules
on the right:
MnO4− → MnO2 + 2 H 2O
55
CHEMISTRY GRADE 12
To balance the H atoms, we add four H + ions on the left:

MnO4− + 4 H + → MnO2 + 2 H 2O
There are three net positive charges on the left, so we add three electrons to the
same side to balance the charges:
MnO4− + 4 H + + 3e − → MnO2 + 2 H 2O
Step 3: We now add the oxidation and reduction half reactions to give the overall
reaction. To equalize the number of electrons, we need to multiply the
oxidation half-reaction by 3 and the reduction
half-reaction by 2 as follows:
3(2 I − → I 2 +2e _ )
2(MnO4− + 4 H + + 3e − → MnO2 + 2 H 2O)
6 I − +2MnO4− + 8 H + + 6e − → 3I 2 + 2 MnO2 + 4 H 2O + 6e _
The electrons on both sides cancel, and we are left with the balanced net ionic
equation:
6 I − +2MnO4− + 8 H + → 3I 2 + 2 MnO2 + 4 H 2O
This is the balanced equation in an acidic medium. However, because the
reaction is carried out in a basic medium, for every H + ion we need to add an
equal number of OH − ions to both sides of the equation:
6 I − +2MnO4− + 8 H + + 8OH − → 3I ü + 2 MnO + 4 H O + 8OH −
Finally, combining the H + and OH − ions to form water, we obtain
6 I − +2MnO4− + 4 H 2O → 3I 2 + 2 MnO2 + 8OH −
Step 4: A final check shows that the equation is balanced in terms of both atoms
and charges
Exercise 2.2
1. 1. Balance the following equation for the reaction in an acidic medium by
the half-reaction method:
a. H 2C2O4 + MnO4− → CO2 + Mn 2+
b. Cr2O7 2− + Fe2+ → Cr 3+ + Fe3+
c. H 5 IO6 + Cr → IO3− + Cr 3+
d. NO − + H O → NO + O
3 2 2 2
e. BrO3 + Fe → Br + Fe3+
− 2 + −
56
Electro chemistry
2.2 ELECTROLYSIS OF AQUEOUS SOLUTIONS

 explain metallic conductivity, electrolytic conductivity and electrolysis
of molten electrolytes
 draw labeled diagrams of an electrolytic cell;
 define preferential discharge
 explain factors that affect preferential discharge.
 describe the effect of nature of the ions on the electrolysis of aqueous
solutions of dil. H SO and NaOH .

2 4
 describe the effect of concentration of the ions on the electrolysis of
dilute and concentrated solutions of NaCl
 describe the effects of types of electrodes on the electrolysis of CuSO4
solution using Ni electrodes and Cu electrodes.
 write electrode half reactions and overall reactions for the electrolysis
of dil. H SO , NaOH , dil NaCl , conc. NaCl and CuSO4 solutions

2 4
 distinguish between molten electrolytes and aqueous electrolytic
solutions,
Before we study the electrolysis of aqueous solutions, let us consider some important
concepts about conductivity. Electrical conductivity is the ability of a substance to
transmit electricity. The substances, which allow the passage of electric current, are
called conductors. Conductors of electricity are further classified into two types depending
on their mode of transport of electrical charges inside them. These are electronic (metallic)
conductors and electrolytic conductors.
Activity 2.2
Form a group and discuss the following points and present your answers to the
class. Your teacher will help you to form groups.
1. How does conduction occur in metals and in electrolytes?
2. What do substances need in order to conduct electricity?
3. Can ionic compounds conduct electricity in the solid state? If your answer is
“No”, why?
Metallic conductors
Metals and alloys conduct electricity due to the movement (mobility) of delocalized outer
57
CHEMISTRY GRADE 12
shell electrons present inside them and are known as electronic conductors (or) metallic
conductors. In metallic conductors
 There is only flow of electrical energy but there is no transfer of matter.

 Electrical conduction through metals does not bring about any chemical transformations.
 Free and mobile electrons of the metallic atoms or their solid solutions such as alloys
are responsible for electrical conductance.
 Conductivity of metal decreases with increase in temperature due to the enhanced
thermal vibration of metal atoms disrupting the movement of electrons passing through
them.
Electrolytic conductor: Electrovalent (or) ionic compounds conduct electricity in their

dissolved state (in solutions) or in their fused state only. These compounds consist of ions
of opposite charges and in aqueous solution they exist as ions. In the presence of applied
electrical field, these ions migrate to respective electrodes exhibiting electrical conductivity
(Figure 2. 1). This mobility of ions is responsible for conduction of electricity through
electrolytes and is referred as electrolytic conduction. In the electrolytic conduction:
• passage of current through electrolytes is accompanied by chemical changes.

• there is actual transfer of matter since ions move towards respective electrodes.
• the conductivity of electrolytes increases with increase in temperature. This is due to
increase with ionic mobility.
Figure 2. 1: Electrical Conductivity Apparatus
Exercise 2.3
1. Which of the following substances are capable of conducting electricity?
Give reason for your answer.
a. Iron b. Sulphur c. Solid sodium chloride d. Molten calcium chloride
58
Electro chemistry
Experiment 2.1
Electrical Conductivity Test
Objective: To classify substances as electrical conductors and insulators.
Materials and chemicals: Copper wire, light bulb, power supply (DC) or dry
cells, scotch tape, distilled water, 1M NaCl solution, 1M H SO solution, 1 M
2 4
CH 3COOH solution, 1 M sugar solution, magnesium ribbon and an iron nail.
Figure 2. 2 (a): Electrical conductivity apparatus for (b) Electrical conductivity

apparatus for
solid materials. liquids and solutions.
Procedure:
1. Polish the strip of copper and connect the two ends of the copper wire as shown
in Figure 2. 2a. Do the same thing for iron nail and magnesium. Record your
observations.
2. Rinse the 100 mL beaker thoroughly with distilled water and fill to the 50 mark
and insert the two ends of the copper wire as shown in Figure
3. Clean the two ends of the copper wire in Figure 2. 2b with distilled water and
insert them into a beaker containing 50 mL of 1 M NaCl solution. Repeat the
same thing for the 1 M H SO , 1 M CH 3COOH and1 M sugar solutions. Re-
2 4
cord your observation. Record your observation.
Results and Discussion:
1. Why is it important to polish the magnesium ribbon and iron nail before use?
2. Classify the materials you used as conductors, strong electrolytes, weak electro-
lytes and non-electrolytes.
3. Label the two ends of the wire in Figure 2. 2b as cathode and anode.
59
CHEMISTRY GRADE 12
Electrochemical cells
An electrochemical cell is a device that can generate electrical energy from the chemical
reactions occurring in it, or use the electrical energy supplied to it to facilitate chemical
reactions in it. These devices are capable of converting chemical energy into electrical
energy, or vice versa. A common example of an electrochemical cell is a standard 1.5-volt
cell which is used to power many electrical appliances such as TV remotes and clocks.
There are two types of electrochemical cells. These are Galvanic cells (also known as
Voltaic cells) and Electrolytic cells
2.2.1 Electrolytic cells
Activity 2.3
Form a group, and discuss each of the following questions. After the
discussion, share your ideas with the rest of the class.
1. Describe the migration of ions during electrolysis?
2. Observe Figure 2.3 and answer the following questions.
Figure 2. 3: Electrolytic cell containing molten sodium chloride.

3. a. Label the anode and the cathode.
b. Indicate the migration of sodium ions and chloride ions.
c. Write the reduction half-reaction, oxidation-half reaction, and the
overall reaction.
60
Electro chemistry
It is possible to construct a cell that does work on a chemical system by driving an electric
current through the system. These cells are called electrolytic cells. Electrolytic cells, like
galvanic cells, are composed of two half-cells-one is a reduction half-cell, the other is
an oxidation half-cell (Figure 2. 4b). The direction of electron flow in electrolytic cells,
however, may be reversed from the direction of spontaneous electron flow in galvanic
cells (Figure 2. 4a), but the definition of both cathode and anode remains the same, where
reduction takes place at the cathode and oxidation occurs at the anode. Because the
directions of both half-reactions have been reversed, the sign, but not the magnitude, of the
cell potential has been reversed.
Electrolytic cells are very similar to voltaic (galvanic) cells in the sense that both require a
salt bridge, both have a cathode and anode side, and both have a consistent flow of electrons
from the anode to the cathode. However, there are also striking differences between the two
cells. The main differences are outlined below:
Table 2.1: comparison of Galvanic Cell / Voltaic and Cell Electrolytic Cell
Galvanic Cell / Voltaic Cell Electrolytic Cell

The redox reactions that take place in these An input of energy is required for the redox
cells are spontaneous in nature. reactions to proceed in these cells, i.e., the
reactions are non-spontaneous.
In these electrochemical cells, the anode These cells feature a positively charged
is negatively charged and the cathode is anode and a negatively charged cathode.
positively charged.
The electrons originate from the species Electrons originate from an external source
that undergoes oxidation. (such as a battery).
Energy released by spontaneous redox Electrical energy is used to derive non
reaction is converted to electrical energy spontaneous redox reaction
Oxidation half reaction Oxidation half reaction
Y → Y + + e− Z − → Z + e−
Reduction half reaction Reduction half reaction
Z + + e− → Z Y + + e− → Y
Overall reaction Overall reaction
Y + Z+ →Y+ + Z (∆G < 0) Y + + Z − → Y + Z (∆G > 0)
61
CHEMISTRY GRADE 12
Figure 2. 4: An electrochemical cell: a) galvanic (voltaic) cell b) electrolytic cell
2.2.2 Preferential Discharge
What does preferential discharge mean?
During electrolysis, the cations being positively charged get attracted towards the negatively
charged electrode (cathode) and anions being negatively charged get attracted towards the
positively charged electrode (anode). If more than one cation or anions reach an electrode,
only one of them preferentially gets discharged at one electrode. Thus, there is a choice
amongst the ions that will get discharged on an electrode. This is called the preferential
discharge of ions during electrolysis. There are different factors that affect preferential
discharge of ions during electrolysis. These are:
Position of ions in the electrochemical series
The reactivity series is a list of metals in decreasing order of their reactivity. It is used
to determine the products of single displacement reactions; whereby metal A will replace
another metal B in a solution if A is higher in the series. Activity series of some of the more
common metals, listed in descending order of reactivity is given in table 2.1.
62
Electro chemistry
Table 2.1: Reactivity series of metals
Activity of Metals Reactivity

Li
K
Displaces H2 gas from cold water, steam and acids
Ba
and forms hydroxides
Sr
Ca
Na
Mg
Al
Zn
Displaces H2 gas from steam and acids and forms
Cr hydroxides but do not displace hydrogen from cold
water.
Fe
Cd
Co
Ni
displaces H2 gas from acids only and forms hydrox-
Sn
ides
Pb
H2 Included for comparison
Cu
Hg
Ag
Un reactive with water or acids.
Pt
Au
When a metal in elemental form is placed in a solution of another metal salt it may be more
energetically feasible for this “elemental metal” to exist as an iron and the “ionic metal” to
exist as the element. Therefore, the elemental metal will “displace” the ionic metal and the
two swap places. A metal can displace metal ions listed below it in the activity series, but
not above. For example, zinc is more active than copper and is able to displace copper ions
from solution
Zn( s ) + Cu 2+ (aq ) → Zn 2+ (aq ) + Cu ( s )
However, silver cannot displace copper ions from solution. This is because silver is found
below copper in the activity series. It is important to distinguish between the displacement
of hydrogen from an acid and hydrogen from water. Sodium is highly active and is able to
63
CHEMISTRY GRADE 12
displace hydrogen from water:
2 Na ( s ) + 2H 2 O(l ) → 2 NaOH (aq ) + H 2 (g)
Less active metals like iron or zinc cannot displace hydrogen from water but do readily
react with acids:
Zn( s ) + 2H 2SO 4 (aq ) → ZnSO4 (aq ) + H 2 (g)
Those metals that can displace H+ ions from acids are easily recognized by their position
above H in the activity series. The boundary between the metals that react with water
and those that don’t is harder to mark. For example, calcium is quite reactive with water,
whereas magnesium does not react with cold water but does displace hydrogen from steam.
A more sophisticated calculation involving electrode potentials is required to make accurate
predictions in this area. The activity series of common cations and anions are given in table
2.2
Table 2.2: The ease of discharge of some common cations and anions.
The ions that are lower in the electrochemical series get discharged in preference to
those above them. For example, if a solution has potassium ions and copper ions, the copper
ions will accept electrons, and get discharged as copper atoms first. The potassium ions will
not be affected. In general, if two or more positive ions migrate to the cathode, the ion lower
64
Electro chemistry
in the series is discharged preferentially. Similarly, if two or more negative ions migrate to
the anode, the ions lower in the series are discharged preferentially.
The concentration of ion
How is concentration of an ion affect preferential discharge?
Higher the concentration of anions in the electrolytic solution, greater is its probability
of being discharged at the anode. For example, a solution of sodium chloride in water
contains two types of anions i.e., the chloride ( Cl − ) ions and the hydroxide ( OH − ) ions.
The hydroxide ions are lower in the electrochemical series than the chloride ions. But if
the concentration of chloride ions is much higher than that of the hydroxide ions, then the
chloride ions get discharged first.
The nature of electrode
How do electrodes affect the preferential discharge of ions?
If the electrode used is inert i.e. made of less reactive material such as graphite, platinum
etc, the electrode does not play any role in deciding the preferential discharge of ion at it.
But when the electrode used is active i,e made of active material such as Cu, Ag, Ni etc it
takes part in the electrode reaction and plays an important role in deciding the ions which
will preferentially be discharged. In such a case, anions migrate to the anode but do not
get discharged, instead the active anode itself loses electrons and forms ions. For example,
in the electrolysis of copper sulphate solutions, using graphite electrodes, oxygen gas is
liberated at the anode and copper metal is deposited at the cathode, as shown below.
_
CuSO (aq) → Cu 2+ (aq)+SO 2 (aq)
4 4
Anode: 4OH − (aq ) → O2 ( g ) + 2 H 2O(l ) + 4e −
_
Cathode: Cu 2+ (aq)+2e → Cu(s)
However, if the electrolysis of copper sulphate solutions is performed using copper

electrodes, the copper electrode at the anode dissolves and copper metal will be deposited
at the cathode, as indicated below.
_
Anode: Cu(s) → Cu 2+ (aq)+2e
_
Cathode: Cu 2+ (aq)+2e → Cu(s)
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CHEMISTRY GRADE 12
Exercise 2.4
1. Define the following terms:
a. preferential discharge
b. inert electrode
c. reactive or active electrode.
2. What gases are liberated at the cathode and anode if concentrated
hydrochloric acid is electrolyzed? Write the reduction half-reaction,
oxidation half-reaction and the overall reaction.
2.2.3 Electrolysis of Some Selected Aqueous Solutions
Activity 2.4
4. Form a group, and discuss each of the following:
1. Prior to electrolysis, why sodium chloride must be in molten state?
2. For the electrolysis of molten KCl , write a balanced equation for the:
a. a anode reaction
b. b cathode reaction
c. c overall reaction
+ − + −
3. Why are H and Cl ions discharged in preference to Na and OH ions
in concentrated sodium chloride solution? After the discussion, share
your ideas with the rest of the class.
Electrolysis is defined as a process of decomposing ionic compounds into their elements
by passing a direct electric current through the compound in an aqueous solution. In the
process of electrolysis, there is an interchange of ions and atoms due to the addition or
removal of electrons from the external circuit. Basically, on passing current, cations move
to the cathode, take electrons from the cathode (given by the supply source-battery), and is
discharged into the neutral atom. The neutral atom, if solid, is deposited on the cathode and
if gas, move upwards. This is a reduction process and the cation is, reduced at the cathode.
At the same time anions, give up their extra electrons to the anode and is oxidized to neutral
atoms at the anode. Electrons released by the anions travel across the electrical circuit and
reach the cathode completing the circuit. Electrolysis involves a simultaneous oxidation
reaction at anode and a reduction reaction at the cathode. During electrolysis, the free
ions furnished by the electrolyte are migrated towards oppositely charged electrodes and
are discharged under electric potential. i.e. Cations migrate towards the cathode and are
reduced.
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Electro chemistry
Anions migrate towards the anode and are oxidized.
Electrolysis of concentrated Sodium Chloride solution (brine solution)

Which ions are discharged at the cathode and anode?
Sodium chloride is dissociated and exists as sodium and chloride ions in aqueous solution.
Electrolysis of sodium chloride is easier in aqueous solution. But, water itself can undergo
reduction and oxidation reactions at different potentials. So, the substance that is oxidized
or reduced is not sodium and chloride ions alone but it may involve the water molecule also.
That is in the concentrated sodium chloride solution there are Na + , Cl − , H + and OH −
ions that compute for preferential discharge. When a potential difference is established
across the two electrodes, Na + and H + ions move towards the cathode, and Cl − and OH −
ions move towards the anode. The reduction reaction that occurs at the cathode does not
produce sodium metal, instead, the H + is reduced as shown in Figure 2. 5. This is because
the reduction potential for water is only −0.83V compared to −2.71V for the reduction of
sodium ions. This makes the reduction of H + preferable because its reduction potential is
less negative.
On the other hand, you might expect H2O to be oxidized in preference to Cl − under standard-
state conditions, However, the potentials are close and over voltages at the electrodes could
alter this conclusion. It is possible, nevertheless, to give a general statement about the product
expected at the anode. Electrode potentials, as you have seen, depend on concentrations. It
turns out that when the solution is concentrated enough in Cl − , Cl2 is the product, but in
dilute solution, O 2 is the product.
Chlorine gas is still produced at the anode.
Cathode (Reduction): 2 H + (aq ) + 2e − → H 2 ( g )
Anode (oxidation): 2Cl − (aq ) → Cl2 ( g ) + 2e −
Over all reaction: 2 H + (aq ) + 2Cl − (aq ) → H 2 ( g ) + Cl2 ( g )

As the overall reaction shows, the concentration of the Cl − ions decrease during electrolysis
and that of the OH − ions increase. Therefore, in addition to H 2 and Cl2 , the useful by-
product NaOH can be obtained by evaporating the aqueous solution at the end of the
electrolysis.
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CHEMISTRY GRADE 12
Figure 2. 5: Electrolysis of brine solution.
Electrolysis of Dilute Sodium Chloride Solution
Activity 2.5
1. For the electrolysis of dilute solution of sodium chloride.
a. List all ions present in the solution.
b. Identify ions that migrate towards the anode and the cathode.
c. Write the electrode half-reactions and overall reaction
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Electro chemistry
Experiment 2.2
Investigating electrolysis of sodium chloride solution
Objective: To electrolyze sodium chloride solution and observe the reaction occur-
ring at the electrodes.
Apparatus and Chemicals: Water, sodium chloride, beakers, measuring cylinder,
graphite electrodes, batteries and connecting wires.
Figure 2. 6: Electrolysis of sodium chloride solution

Procedure:
1. Prepare 0.1 M sodium chloride solution.
2. Transfer the solution to the beaker.
3. Immerse the graphite electrodes in the sodium chloride solution.
4. Arrange the setup as shown in the Figure 2. 6
Results and Discussion:
1. What do you observe at the surface of the electrodes?
2. Identify the cathode and anode in the Figure 2. 6.
3. Name the gases evolved at the cathode and anode.
4. Write the equations for anode and cathode reactions
Electrolysis of Dilute Sulphuric Acid Solution

Which ions are discharged at the cathode and anode?
Dilute sulfuric acid contains water. The ions present in this mixture are H + and OH − ions
(from water) and H + and SO4 2− ions from the sulfuric acid. When a potential difference
is applied across the two electrodes (anode and cathode), the H + ions are attracted to the
69
CHEMISTRY GRADE 12
cathode and the two negative ions ( OH − and SO4 2− )are attracted to the anode. At the
cathode H + is discharged and at the anode OH − ions are preferentially discharged because
the OH − ion is below the SO4 2− ion in the electrochemical series. The electrode reactions
are:
Anode (oxidation): 4OH − (aq ) → 2 H 2O(l ) + O2 ( g ) + 4e −
Cathode (reduction): 4 H + (aq ) + 4e − → 2 H 2 ( g )

Overall reaction: 2 H 2O( g ) → 2 H 2 ( g ) + O2 ( g )
Note that the electrolysis of dilute NaCl and dilute H 2 SO4 solutions results in the
decomposition of water to oxygen and hydrogen gases. .
Water has very low conductivity and the small amount of ionic sodium chloride helps the
ionic conductivity of the solution. In small concentration, the electrolysis of water becomes
more predominant yielding hydrogen at cathode and oxygen at the anode.
Electrolysis of Copper (II) Sulphate Using Inert Electrodes

Which ions preferentially discharged at the cathode and anode if copper (II) sulphate solu-
tions electrolyzed, using platinum (inert) electrodes?
Electrolyte CuSO4 dissociates in to Cu 2+ and SO4 2− ions along with H + and OH − ions in the
aqueous solution. Cu 2+ ion preferentially discharged because it has higher reduction potential
than H + . On the other hand, OH − has higher oxidation potential than SO4 2− , so it gets
preferentially oxidized. Electrode reactions are:
At cathode (Reduction): 2Cu 2+ (aq ) + 4e − → 2Cu ( s )
At anode (oxidation): 4OH − (aq ) → 2 H 2O(l ) + O2 ( g ) + 4e −

2+ −
Overall reaction: 2Cu (aq ) + 4OH (aq ) → 2Cu ( s ) + 2 H 2O(l ) + O2 ( g )
Hence, Cu at cathode and O2 at anode are produced by electrolysis of aqueous CuSO4 with
inert electrodes. Since copper ions are deposited at the cathode, and hydroxide ions at the
anode, the solution becomes acidic due to the formation of H 2 SO4 using H + and SO4 2−
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Electro chemistry
Electrolysis of Copper (II) Sulphate Solution Using Copper Electrodes
Activity 2.6
1. Are the copper electrodes reactive or inert in the electrolysis of CuSO
solution?
2. Write the reactions occurring at the anode and at the cathode during the
electrolysis of CuSO4 solution, using copper electrodes.
3. What is the net result of the electrolysis of CuSO4 solution, using copper
electrodes?
The use of copper electrodes illustrates how copper is refined industrially. Replacing the
inert Electrodes with clean copper plates produces a different anode reaction. At the anode,
no oxygen is produced, rather the copper anode dissolves. On the other side of the half
reaction a deposit of copper forms on the cathode. The half-cell reactions are:
2+ −
Anode reaction: Cu ( s ) → Cu (aq ) + 2e
2+ −
Cathode reaction: Cu (aq ) + 2e → Cu ( s )
During this electrolysis, the mass gained of copper at the cathode is equal to the mass lost
at the anode.
Exercise 2.5
1. For the electrolysis of dilute NaOH solution,
a. write the balanced chemical equations for the reduction half-reaction
and oxidation half reactions.
b. write the balanced overall cell reaction.
2. What happens to the concentration of the dilute ü 2 4 solution after
electrolysis?
3. Does the concentration of CuSO4 increase, decrease or remain the same
after the electrolysis of CuSO4 , using inert electrodes? Explain.
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CHEMISTRY GRADE 12
2.3 QUANTITATIVE ASPECTS OF ELECTROLYSIS

 state Faraday’s first law of electrolysis;
 write the mathematical expressions for the Faraday’s first law of
electrolysis;
 do calculations related to Faraday’s first law of electrolysis;
 state Faraday’s second law of electrolysis;
 write the mathematical expressions for Faraday’s second law of
electrolysis; and
 do calculations related to Faraday’s second law of electrolysis.
Is it possible to calculate the amount of product formed at the electrodes?
The quantitative treatment of electrolysis was developed primarily by Michael Faraday in

the year 1834. His early research on electrolysis led him to propose a relationship between
the amount of current passed through a solution and the amount of substance decomposed
or produced by the current
2.3.1 Faraday’s First Law of Electrolysis
Faraday’s First Law of Electrolysis states that when an electrolyte, either in molten state
or solution state is electrolyzed, the mass of a substance (m) deposited or dissolved at
electrodes is directly proportional to the quantity of electricity (coulombs, Q ) passed
through the electrolyte.
Mathematically,
m∝ Q or
m = zQ
where, z is a proportionality constant called electrochemical equivalent
E
Since z = & Q = It
F
EIt
We can also rewrite the equation as: m =
F
72
Electro chemistry
Where:
E = equivalent weight of substance

F = Faraday Constant (96,500 Coulombs)
m = mass of substance
I = current in amperes
t = time required
Molecular mass ( M )
equivalent weight of a substance E =
Valence (n)
MIt
Thus, m =
nF
For example, in the electrolysis of molten NaCl , the cathode reaction tells us that one Na
atom is produced when one Na + ion accepts an electron from the cathode. To reduce 1 mole
of Na + ions, we must supply one mole of electrons (6.02 × 1023 electrons) to the cathode.
Example 2.3
How many moles of chlorine, magnesium and aluminum are formed when 2, 2 and
3 moles of charge are passed through three different solution containing chloride,
magnesium and aluminum ions respectively?
Solution:
The stoichiometry of the anode reaction shows that oxidation of two Cl − ions
yield one chlorine molecule and releases two electrons. Therefore, the formation
of 1 mole of chlorine results in 2 moles of electrons supplied by the Cl − ions to the
anode. Similarly, it takes 2 moles of electrons to reduce 1 mole of Mg 2+ ions and
3 moles of electrons to reduce 1 mole of Al 3+ ions:
2Cl − (aq ) → Cl2 ( g ) + 2e −
Mg 2+ (aq ) + 2e − → Mg ( s )
Al 3+ (aq ) + 3e − → Al ( s )
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CHEMISTRY GRADE 12
Example 2.4
Calculate the mass of calcium metal and chlorine gas that can be produced when
a current of 0.452 A is passed through molten CaCl2 for 1.5 h.
Solution:
In solving electrolysis problems of this type, the first step is to determine which
species will be oxidized at the anode and which species will be reduced at the
cathode. Here the choice is straight forward because we only have Ca 2+ and Cl −
ions in molten CaCl2 . Thus, we write the half and overall reactions as:
Anode (Oxidation): 2Cl − (aq ) → Cl2 ( g ) + 2e −
Cathode (Reduction): Ca 2+ (aq ) + 2e − → Ca ( s )
Over all Reaction: Ca 2+ (aq ) + 2Cl − (aq ) → Ca ( s ) → Cl2 ( g )
The quantities of calcium metal and chlorine gas formed depend on the number of
electrons that pass through the electrolytic cell, which in turn depends on current
× time or charge.
Charge (Q) = current (I) in A × time (t) in s
Q =I ×t = (0.452 A) × (1.5 × 60 × 60 s)
= 2.44 × 103 A s = 2.44 × 103 C
1 mol e– = 96,500 C
x = 2.44 × 103 C
2.44 × 103 C x 1 mol e −

⇒x= =0.0253 mol e −
96,500 C
2 moles of electrons are required to produce 1 mole, or 40 g, of calcium metal at
the cathode. Hence, the mass of calcium formed is
2 mol e– = 1 mole Ca = 40.08 g Ca
0.0253 mol e– = x
0.0253 mol e − x 40.08 g Ca

=⇒x = 0.507 g Ca
2 mol e −
The anode reaction indicates that 1 mole, or 71 g, of chlorine is produced by
giving 2 moles of electrons to the anode. Hence, the mass of chlorine gas formed is
2 mol e–= 71 g Cl2= 1 mole Cl2
0.0253 mol e–= x
0.0253 mol e − x 71 g Cl2

=⇒x = 0.898 g Cl2
2 mol e −
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Electro chemistry
Exercise 2.6
1. Calculate the volume of H 2 and O2 gases at 25°C and 1.00 atm that will be
collected at the cathode and anode, respectively, when an aqueous solution
of Na2 SO4 is electrolyzed for 2 hours with 10 amperes current.
2. Calculate the mass of copper and volume of oxygen (at 25°C and 760
mmHg) that would be produced by passing a current of 0.5 A through a
CuSO4 solution between Pt electrodes for 3 hours.
3. What mass of aluminum is deposited electrolytically in 30 minutes by a
current of 40 A?
2.3.2 Faraday’s Second Law of Electrolysis
Faraday’s second law of electrolysis states that” The masses of different substances, liberated
or dissolved by the same amount of electricity, are proportional to their equivalent masses.”
When the same quantity of electricity is passed through several electrolytic solutions
connected in series, then the masses of the different materials liberated or dissolved (m1, m2,
m3...) at the respective electrodes are in the ratio of their equivalent masses (E1, E2, E3...).
Mathematically, m α E or m1 α E1 , m2 α E2 , and m3 α E3 etc
Replacing the proportionality by the proportionality constant, the equation become
m1 m2 m3 m1 m2
= = = k =
E1 E2 E3 or E E2
1
The law can be illustrated by passing the same quantity of electric current through three
solutions containing H 2 SO4 , CuSO4 and AgNO3 , connected in series, as shown in Figure
2. 7 .
Figure 2. 7: Solutions connected in series to a battery.
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CHEMISTRY GRADE 12
In the first solution, hydrogen and oxygen are liberated. In the second solution copperis
deposited and in the third, silver is deposited.
mass of hydrogen mass of copper mass of silver

= =
equivalent mass of Hydrogen equivalent mass of copper equivalent mass of silver
Example 2.5
1. Calculate the mass of copper deposited by the electrolysis of CuSO4 solution placed
in series with a silver nitrate solution, when 0.108 g of Ag is being deposited.
Solution: The equivalent mass of silver and copper can be obtained from their
reduction half-reaction:
108 g / mol
Ag + (aq ) + 1e − → Ag ( s=
), E Ag = 108 g / eq
1
63.5 g / mol
Cu 2+ (aq ) + 2e − → Cu (=
s ), ECu = 31.75 g / eq
2
The mass of Ag is 0.108 g, and you are asked to find the mass of copper.
mCu m Ag
ECu m Ag
⇒ m = =
E Ag ECu Cu E Ag
31.75 g / eq x 0.108 g
= = 0.032 g of Cu is deposited
108 g / eq
Exercise 2.7
1. Two cells are connected in series. One contains AlCl3 , and the other
contains AgNO3 as the electrolytes. What mass of Ag is deposited when 18
g of Al is deposited at cathode?
2. 0.2 moles of electrons are passed through three electrolytic cells in series
that contain silver ions, zinc ions and iron (III) ions. How many grams of
each metal will be deposited at cathode?
2.4 INDUSTRIAL APPLICATION OF ELECTROLYSIS

 mention the industrial applications of electrochemistry;
 explain electroplating and electro refining;
 demonstrate copper refining; and
 explain how electrolysis is used in the production of some metals,
nonmetals and compounds
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Electro chemistry
Electrolysis has many industrial applications. Some of them are the following.
The production of chemicals

Can you mention list of chemicals that can be produced by the electrolysis?
Many chemicals can be produced using electrolysis. For example, the chlorine-alkali
industry is an important part of the chemical industry, which produces chlorine and sodium
hydroxide through the electrolysis of the raw material brine. The reactions that take place
at the electrodes (when graphite electrodes are used) are as follows:
Anode reaction: 2Cl − (aq ) → Cl2 ( g ) + 2e −
Cathode reaction: 2 H 2O(l ) + 2e − → H 2 ( g ) + 2OH − (aq )
Overall cell reaction is: 2 NaCl (aq ) + 2 H 2O(l ) → 2 Na + (aq ) + 2OH − (aq ) + Cl2 ( g ) + H 2 ( g )
Electro synthesis of metals

Electro synthesis is the method of producing substances through electrolysis reactions.
Extraction of Metals
Activity 2.7
Discuss each of the following questions. After the discussion, share your
ideas with your classmates.
1. List active metals that can be extracted from their compounds by
electrolysis.
2. Explain why electrolytic reduction rather than chemical reduction is often
used to
obtain active metals from their compounds.
3. Why are molten metal chlorides used as electrolytes rather than using other
molten salts?
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CHEMISTRY GRADE 12
Electrolytic refining of Metals
Activity 2.8
Form a group. Discuss each of the following questions. After the discussion,
share your ideas with the rest of the class.
1. Define electro refining.
2. What are the purposes of electro refining?
3. Describe the electro refining of copper. Include the appropriate chemical
equations.
Electroplating of Metals
Experiment 2.3
Electroplating an iron key with copper metal
Objective: To conduct Electroplating of an iron key with copper metal
Apparatus and chemicals: Beaker, sand paper, copper wire, power supply (DC) or
dry cells, distilled water, 1M copper sulphate solution, 1 M H 2 SO4 solution, copper
rode and an iron key
Figure 2. 8: Electroplating of an iron object with copper
78
Electro chemistry
Procedure:
1. Dissolve two teaspoonfuls of CuSO4 in 250 mL of distilled H 2O in a clean and
dry beaker. To increase conduction, add a few drops of dilute H 2 SO4 to CuSO4
solution. Take a copper plate of 10 cm x 4cm size and a door key made of iron.
Use sandpaper to clean the copper plate and iron key. Rinse the copper plate and
iron key with water and dry them.
2. Place the cleaned copper plate in the CuSO4 solution and connect it to the
positive terminal of a battery as shown in Figure 2. 8.This copper plate becomes
the anode or positive electrode.
3. Place the clean iron key in the CuSO4 solution at a small distance from the
copper plate and connect the negative terminal of a battery to the iron key. This
iron key becomes the cathode or negative electrode.
4. Switch on the electric current by closing the switch. Allows the current to pass
for about 15 minutes.
5. Remove the copper plate and iron key from the CuSO4 solution.
1. What are the purposes of electroplating?
2. Why is it important to polish the copper plate and iron key before use?
3. What do you observe from the surface of the iron key?
4. What will happen to the free copper ions in the CuSO4 solution?
5. What will happen to the copper plate connected to the positive terminal of the
battery?
Electroplating is the process of plating one metal onto another by hydrolysis, most commonly
for decorative purposes or to prevent corrosion of a metal. There are also specific types of
electroplating such as copper plating, silver plating, and chromium plating. Electroplating
allows manufacturers to use inexpensive metals such as steel or zinc for the majority of the
product and then apply different metals on the outside to account for appearance, protection,
and other properties desired for the product. In the process of electroplating, an external
source of electric current is usually applied. This takes place in an electrolytic cell. The
metal on which electroplating takes place is made the cathode (negative terminal) while
the metal which is going to be plated as a layer on the metal is made the anode (positive
terminal). The salt solution of the metal which is to be deposited is taken as electrolyte.
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CHEMISTRY GRADE 12
Many metals, such as copper, zinc, tin, nickel, silver, gold etc. are refined by electrolysis.
In this process, the impure metal is made the anode and a thin strip of pure metal is made
the cathode. The solution of the metal salt is used as an electrolyte. When current passes
through electrolyte, the pure metal from the anode dissolves into the electrolyte. An
equivalent amount of pure metal from the electrolyte is deposited on the cathode. The
insoluble impurities settle down at the bottom of the anode and are known as anode mud
whereas the soluble impurities go into the solution (Figure 2. 9). For example: In the
electrolytic refining of copper, the electrolyte is a solution of acidified CuSO4 . The anode
is impure copper, whereas the cathode is a strip of pure copper. On passing electric current,
pure copper is deposited on the cathode.
Figure 2. 9: Purification of Copper by Electrolysis
During this process, the size of the impure copper anode decreases and that of the pure
copper cathode increases.
Electrosynthesis of Nonmetals
Activity 2.9
Form a group and discuss each of the following questions. After the
1. List nonmetals and compounds that are prepared by electrolysis.
2. Write the cathode and anode reactions during the electrolysis of molten
mixture of potassium fluoride and hydrogen fluoride.
3. Why is a small amount of solute added in the electrolysis of water?
80
Electro chemistry
Electrosynthesis of compounds
An example of electrolysis for the synthesis of compounds is the electrolysis of MnSO4 in
a sulfuric acid solution to produce MnO2.MnO2 occurs naturally in the form of the mineral
pyrolusite, but this mineral is not easily used due to the nature of its size and lattice structure.
However, MnO2 can be obtained in a different way, through the electrolysis ofMnSO4 in a
sulfuric acid solution.
Oxidation : Mn 2+ + 2 H 2O → MnO2 + 4 H + + 2e −
Reduction : 2 H + + 2e − → H 2
Ovcera llreaction : Mn 2+ + 2 H 2O → MnO2 + 2 H + + H 2
Activity 2.10
1. List compounds that are prepared by electrolysis.
2. Write the oxidation half reaction, reduction half reaction and overall
reaction for compound’s you mention in question number 1.
2.5 VOLTAIC CELLS

 define Voltaic cell and salt bridge;
 define electrode potential and cell potential;
 explain how standard electrode potential is measured;
 describe the reactivity of metal from its position in the activity series or
electromotive series;
 decide whether a given redox reaction is spontaneous or not;
 explain the effect of concentration on cell potential;
 mention the different types of Voltaic cells;
 give examples of each type of Galvanic cell;
 describe how a hydrogen-oxygen fuel cell operates;
 distinguish between primary and secondary cells;
 identify the cathode, anode and electrolyte of a given Galvanic cell;
 compare and contrast electrolytic and Galvanic cells;
 explain metallic corrosion in terms of redox reactions;
 explain the negative effects of corrosion; and
 explain the different methods of the prevention of corrosion.
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CHEMISTRY GRADE 12
What makes a Galvanic cell different from an electrolytic cell?
Construction of Voltaic Cells (Zn-Cu voltaic Cell)
Activity 2.11
1. Describe the basic features of an electrochemical cell. Why are the two
components of the cell separated from each other?
2. Below the following chemical reaction is given,
Mg ( s ) + 2 H + (aq ) → Mg 2+ (aq ) + H 2 ( g )
a. write equations for the oxidation and reduction half-reactions.
b. which half-reaction occurs in the anode compartment and in the cathode
compartment?
When a piece of zinc metal is placed in a CuSO4 solution, Zn is oxidized to Zn 2+ ions while
Cu 2+ ions are reduced to metallic copper.
Zn( s ) + Cu 2+ (aq ) → Zn 2+ (aq ) + Cu ( s )
The electrons are transferred directly from the reducing agent ( Zn ) to the oxidizing agent (
Cu 2+ ) in solution. However, if we physically separate the oxidizing agent from the reducing
agent, the transfer of electrons can take place via an external conducting medium (a metal
wire). As the reaction progresses, it sets up a constant flow of electrons and hence generates
electricity (that is, it produces electrical work such as driving an electric motor).
The experimental apparatus for generating electricity through the use of a spontaneous
reaction is called a galvanic cell or voltaic cell. (Figure 2. 10) shows the essential components
of a galvanic cell. A zinc bar is immersed in a ZnSO4 solution, and a copper bar is immersed
in a CuSO4 solution. The cell operates on the principle that the oxidation of Zn to Zn 2+ and
the reduction of Cu 2+ to Cu can be made to take place simultaneously in separate locations
with the transfer of electrons between them occurring through an external wire. The zinc
and copper bars are called electrodes. This particular arrangement of electrodes ( Zn and
Cu ) and solutions ( ZnSO4 and CuSO4 ) is called the Daniell cell. By definition, the anode
in a galvanic cell is the electrode at which oxidation occurs and the cathode is the electrode
at which reduction occurs. For the Daniell cell, the half-cell reactions, that is, the oxidation
and reduction reactions at the electrodes, are
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Electro chemistry
Oxidation: Zn( s ) → Zn 2+ (aq ) + 2e −

Reduction: Cu 2+ (aq ) + 2e − → Cu ( s )
Overall Reaction: Zn( s ) + Cu 2+ (aq ) → Zn 2+ (aq ) + Cu ( s )
Because zinc tends to lose electrons more readily than copper, zinc atoms in the zinc
electrode lose electrons to produce zinc ions. These electrons flow through the external
circuit to the copper electrode, where they react with the copper ions in that half-cell to
deposit copper metal atoms. The net result is that zinc metal reacts with copper ions to
produce zinc ions and copper metal, and electric current flows through the external circuit.
Note that unless the two solutions are separated from each other, the Cu 2+ ions will react
directly with the zinc bar and no useful electrical work will be obtained.
To complete the electrical circuit, the solutions must be connected by a conducting medium
through which the cations and anions can move from one electrode compartment to the
other. This requirement is satisfied by a salt bridge, which, in its simplest form, is an
inverted U tube containing an inert electrolyte solution, such as KCl , KNO3 or NH 4 NO3 ,
whose ions will not react with other ions in solution or with the electrodes (Figure 2. 10).
During the course of the overall redox reaction, electrons flow externally from the anode (
Zn electrode) through the wire and light bulb to the cathode ( Cu electrode).
In the solution, the cations ( Zn 2+ , Cu 2+ , and K + ) move toward the cathode, while the
anions ( SO4 2− and Cl − ) move toward the anode. Without the salt bridge connecting the two
solutions, the buildup of positive charge in the anode compartment (due to the formation
of Zn 2+ ions) and negative charge in the cathode compartment (created when some of the
Cu 2+ ions are reduced to Cu ) would quickly prevent the cell from operating.
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CHEMISTRY GRADE 12
Figure 2. 10: Daniell cell.
Cell diagram (Cell Notation)

The conventional notation for representing the components of a voltaic cells or galvanic
cells is the cell diagram. For example cell notation for the Daniell cell shown in Figure 2.
10is given by:
Zn( s ) | Zn 2+ (aq ) || Cu 2+ (aq ) | Cu ( s )

You will use the following generally accepted conventions in writing cell notation.
• The components of the anode compartment (oxidation half-cell) are written to the left
of the components of the cathode compartment (reduction half-cell).
• A boundary between different phases (an electrode and a solution) is represented by
a single vertical line. For example, Zn( s ) | Zn 2+ (aq ) indicates that solid Zn is in a
different phase with aqueous Zn 2+
• The boundary between half-cell compartments, commonly a salt bridge, is represented
by a double vertical line. Species in aqueous solution are placed on either side of the
double vertical line. Different species within the same solution are separated from each
other by a comma.
For example, the notation for the voltaic cell shown in the following reaction is:
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Electro chemistry
Oxidation half reaction: 2 I − (aq ) → I 2 ( s ) + 2e −
Reduction half reaction: MnO4 − (aq ) + 8 H + (aq ) + 5e − → Mn 2+ (aq ) + 4 H 2O(l )

Over all (Cell) reaction:
MnO4 − (aq ) + 16 H + (aq ) + 10 I − (aq ) → 2 Mn 2+ (aq ) + 5 I 2 ( s ) + 8 H 2O(l )
graphite | I − (aq ) | I 2 ( s ) || MnO4 − (aq ), H + (aq ), Mn 2+ (aq ) | graphite
That is, in the cathode compartment, MnO4 − , H + and Mn 2+ ions are in an aqueous solution
with solid graphite (inert electrode) immersed in it.
• If needed, the concentrations of dissolved components are given in parentheses; for
example, if the concentrations of Zn 2+ and Cu 2+ are 1M, we write
Zn( s ) | Zn 2+ (1M ) || Cu 2+ (1M ) | Cu ( s ) or
Zn( s ) | Zn 2+ (aq,1M ) || Cu 2+ (aq,1M ) | Cu ( s )
anode → Zn| Zn 2 + (aq, 1.00M) || Cu 2+ (aq, 1.00M)|Cu(s) ← cathode

Oxidation half reaction salt Reduction half reaction
bridge|
• Half-cell components usually appear in the same order as in the half-reaction, and
electrodes appear at the far left (anode) and far right (cathode) of the notation.
• Ions in the salt bridge are not part of the reaction so they are not in the notation.
The notation for any Galvanic cell has the following form:
anode | anode electrolyte (M) || cathode electrolyte (M) | cathode
Every redox reaction is the sum of an oxidation half-reaction and a reduction half reaction
written in such a way as to cancel out the electrons by suitably multiplying the half-reactions
by the minimum integers.
Example 2.6
Write the cell notation for a Galvanic cell, for the cell reaction:
Cr ( s ) + 3 Ag + (aq ) → Cr 3+ (aq ) + 3 Ag ( s )
Assume that the solution concentrations are 0.20 M
Solution:
Write the oxidation half-reaction and the reduction half-reaction separately.
Oxidation half-reaction (anode): Cr ( s ) → Cr 3+ (aq ) + 3e −
Reduction half-reaction (cathode): Ag + (aq ) + e − → Ag ( s )
The cell notation is Cr ( s ) | Cr 3+ (0.20 M ) || (0.020 M ) Ag + | Ag ( s )
85
CHEMISTRY GRADE 12
Exercise 2.8
1. Write the cell notation for a Galvanic cell consisting of an Al electrode
placed in 1M Al ( NO3 )3 solution and a Ag electrode placed in a 1 M AgNO3
solution.
2. Explain the use of a salt bridge.
Measuring Standard electrode Potentials

A cell potential is a measure of the driving force of the cell reaction. This reaction occurs in
the cell as separate half-reactions: an oxidation half-reaction and a reduction half-reaction.
The general forms of these half-reactions are
Anode (Oxidation): Re duction Species → Oxidized Species + ne −

Cathode (Reduction): Oxidized Species + ne − → Re duction Species
Just as the overall cell reaction can be thought of as the sum of two half-cell reactions, the
measured electrode potential of the cell can be treated as the sum of the electrical potentials
at the Zn and Cu electrodes. Knowing one of these electrode potentials, we could obtain
the other by subtraction. It is impossible to measure the potential of just a single electrode,
but if we arbitrarily set the potential value of a particular electrode at zero, we can use it
to determine the relative potentials of other electrodes. The hydrogen electrode, shown in
Figure 2. 11, serves as the reference for this purpose. In the hydrogen electrode, hydrogen
gas is bubbled into a hydrochloric acid solution at 25°C. The platinum electrode has two
functions.
First, it provides a surface on which the dissociation of hydrogen molecules can take place:
+ −
ü 2 →2 +2
Second, it serves as an electrical conductor to the external circuit.
Under standard-state conditions (when the pressure of H 2 is 1 atm and the concentration
of the HCl solution is 1M), the potential for the reduction of H + at 25°C is taken to be
exactly zero:
2 H + (1M ) + 2e − → H 2 (1 atm), E0 =
0V
The superscript “o” denotes standard-state conditions, and E° is the standard reduction
potential, or the voltage associated with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm. Thus, the standard reduction potential of the hydrogen
electrode is defined as zero. The hydrogen electrode is called the standard hydrogen
electrode (SHE)
86
Electro chemistry
The standard hydrogen electrode(SHE) consists of a platinum electrode that has H 2 gas
at 1 atm bubbling through it and is immersed in 1 M strong acid, H + (aq ) or H 3O + (aq )

(Figure 2. 11). Thus, the reference half-reaction is
2 H + (aq; 1M ) + 2e − → H 2 ( g ; 1 atm), E 0 reference =

0.00V
Figure 2. 11 The Standard Hydrogen Electrode (SHE)
We can use the SHE to measure the potentials of other kinds of electrodes. To find an
unknown standard electrode potential (E0unknown), we construct a voltaic cell consisting of
this reference half-cell and the unknown half-cell. Since E0reference is zero, the overall E0cell
gives E0unknown.
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CHEMISTRY GRADE 12
Depending on the unknown half-cell, the reference half-cell can be the anode or the cathode:
• When H 2 is oxidized, the reference half-cell is the anode, and so reduction occurs
at the unknown half-cell:
E0
= E0 − E0
cell cathode anode
= E 0 −E 0
unknown reference
= E0 − 0.00V
unknown
= E0
unknown
When H 2 is reduced, the reference half-cell is the cathode, and so oxidation occurs
at the unknown half-cell:
= E0 E0 − E0
cell cathode anode
= E0 − E0
reference unknown
= 0.00V − E 0
unknown
= −E 0
unknown
Figure 2.12 shows a voltaic cell that has the Zn( s ) | Zn 2+ half-reaction in one compartment
and the H + | H 2 (or H 3O + | H 2 ) half-reaction in the other. The zinc electrode is negative
relative to the hydrogen electrode, so we know that the zinc is being oxidized and is the
anode and the SHE is the cathode. .
The cell notation is
Zn( s ) | Zn 2+ (1M ) || H + (1M ) | H 2 (1 atm) | Pt ( s )
Figure 2. 12: A cell consisting of a zinc electrode and a hydrogen electrode.
88
Electro chemistry
As mentioned earlier, the Pt electrode provides the surface on which the reduction takes
place. When all the reactants are in their standard states (that is, H 2 at 1 atm, H + and Zn 2+
ions at 1 M), the electromotive force (EMF) of the cell is 0.76 V at 25°C. We use this value
to find the unknown standard electrode potential, E0zinc:
We can write the half-cell reactions as follows:
Anode (Oxidation): Zn( s ) → Zn 2+ (1M ) + 2e −
Cathode (Reduction) : 2 H + (1M ) + 2e − → H 2 (1M )
Overall reaction: Zn( s ) + 2 H + (1M ) → Zn 2+ (1M ) + H 2 (1M )
By convention, the standard EMF of the cell, E0cell, which is composed of a contribution
from the anode and a contribution from the cathode, is given by
E0
= E0 − E0
cell cathode anode
where both E°cathode and E°anode are the standard reduction potentials of the electrodes. For
the Zn-SHE cell, we write
0 0 0
=
E cell E + −E
H / H2 Zn2+ / Zn
0
0.76 V = 0−E
Zn2+ / Zn
where the subscript H + / H 2 means 2 H + + 2e − → H 2 and the subscript Zn 2+ / Zn means
Zn 2+ + 2e − → Zn .Thus, the standard reduction potential of zinc, E 0 2+ , is ─ 0.76 V

Zn / Zn
Note that we write the reaction as a reduction, even though it occurs in reverse as oxidation.
Whenever we assign a potential to a half-reaction, we write the reaction as a reduction.
The standard electrode potential of copper can be obtained in a similar fashion, by using a
cell with a copper electrode and a SHE (Figure 2. 13). In this case, the copper electrode is
the cathode because its mass increases during the operation of the cell, as it is consistent
with the reduction reaction:
89
CHEMISTRY GRADE 12
Figure 2.13: A cell consisting of a copper electrode and a hydrogen electrode
The cell notation is
Pt ( s ) | H 2 (1 atm) | H + (1M ) || Cu 2+ (1M ) | Cu ( s )
and the half-cell reactions are
Anode ( Oxidation): H 2 (1 atm) → 2 H + (1M ) + 2e −
Cathode (Reduction): Cu 2+ (1M ) + 2e − → Cu ( s )
Overall Reaction: H 2 (1 atm) + Cu 2+ (1M ) → 2 H + (1M ) + Cu ( s )
Under standard-state conditions and, the EMF of the cell is 0.34 V, so we write
E0
= E0 − E0
cell cathode anode
0 0
=
0.34 V E − E
Cu2+ /Cu H + / H2
0
=
0.34 V E − 0
Cu2+ /Cu
0
E = 0.34 V
Cu2+ /Cu
In this case, the standard reduction potential of copper, E 0 , is 0.34 V, where the
Cu2+ /Cu
subscript means
90
Electro chemistry
Cu 2+ + 2e − → Cu
For the Daniell cell shown in Figure 2.10, we can now write
Anode(Oxidation): Zn( s ) → Zn 2+ (1M ) + 2e −
Cathode(Reduction): Cu 2+ (1M ) + 2e − → Cu ( s )
Overall Reactio: Zn( s ) + Cu 2+ (1M ) → Zn 2+ (1M ) + Cu ( s )
The EMF of the cell is
0 0 0
=
E cell E cathode − E anode
0 0
=
0.34 V E − E
Cu2+ /Cu Zn2+ / Zn
= 0.34 V ─ (─ 0.76 V)
= 1.10 V
we can use the sign of E° to predict the extent of a redox reaction.
• A positive E° means the redox reaction will favor the formation of products at
equilibrium.
• A negative E° means that more reactants than products will be formed at equilibrium.
The standard reduction potentials for other half-reactions are established in the way that we
did for the Cu 2+ / Cu half-reaction. The standard reduction potentials of some of the half-
reactions are given in Table 2.2
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CHEMISTRY GRADE 12
Table 2.2: Standard Reduction Potential in Aqueous Solution at 25°C.
For all half-reactions the concentration is 1 M for dissolved species and the pressure is 1
atm for gases. These are the standard-state values
1. The E° values apply to the half-cell reactions as read in the forward (left to right)
direction.
2. The more positive E° is, the greater the tendency for the substance to be reduced. For
example, the half-cell reaction
92
Electro chemistry
F2 (1 atm) + 2e − → 2 F − (1M ), E 0 =
2.87 V
has the highest positive E° value among all the half-cell reactions. Thus, is the strongest
oxidizing agent because it has the greatest tendency to be reduced. At the other extreme is
the reaction
Li + (1M ) + 2e − → Li ( s ), E 0 =− 3.05 V
which has the most negative E° value. Thus, Li + is the weakest oxidizing agent because it
is the most difficult species to reduce. Conversely, we say that F2 is the weakest reducing
agent and Li metal is the strongest reducing agent. Under standard-state conditions, the
oxidizing agents (the species on the left-hand side of the half-reactions in Table 2.1increase
in strength from bottom to top and the reducing agents (the species on the right-hand side
of the half-reactions) increase in strength from top to bottom.
3. The half-cell reactions are reversible. Depending on the conditions, any electrode can
act either as an anode or as a cathode. Earlier we saw that the SHE is the cathode ( H +
is reduced to H 2 ) when coupled with zinc in a cell and that it becomes the anode ( H 2
is oxidized to H + ) when used in a cell with copper.
4. Under standard-state conditions, any species on the left of a given half-cell reaction
will react spontaneously with a species that appears on the right of any half-cell
reaction located below it in Table 2.2. This principle is sometimes called the diagonal
rule. In the case of the Daniell cell,
Cu 2+ (1M ) + 2e− → Cu ( s ), E0 =
0.34 V
Zn 2+ (1M ) + 2e− → Zn( s ), E0 =
−0.76 V
We see that the substance on the left of the first half-cell reaction is Cu 2+ and the substance
on the right in the second half-cell reaction is Zn . Therefore, as we saw earlier, Zn
spontaneously reduces
Cu 2+ to form Zn 2+ and Cu .The diagonal line shows that Cu 2+ is the oxidizing agent and
Zn is the reducing agent.
5. Changing the stoichiometric coefficients of a half-cell reaction does not affect the
value of Eored, because electrode potentials are intensive properties. This means that
the value of Eored is unaffected by the size of the electrodes or the amount of solutions
present but is dependent on the concentration of the solutions and the pressure of a
gas. For example:
I 2 ( s ) + 2e − → 2 I − (1M ), E 0 red =+ 0.53 V

but E0 does not change if we multiply the half-reaction by 2
93
CHEMISTRY GRADE 12
2 I 2 ( s ) + 4e − → 4 I − (1M ), E 0 red =+ 0.53 V

6. The sign of Eored changes, but its magnitude remains the same when we reverse a
reaction.
Example 2.7
1. A galvanic cell consists of a Mg electrode in a 1.0 M Mg ( NO3 ) 2 solution and
a Ag electrode in a 1.0 M AgNO3 solution. Calculate the standard emf of
this cell at 25°C. Is this reaction spontaneous?
Solution: At first it may not be clear how to assign the electrodes in the galvanic
cell. From Table 2.1we write the standard reduction potentials of Ag and Mg
apply the diagonal rule to determine which is the anode and which is the cath-
ode.
The standard reduction potentials are

Ag + (1.0 M ) + e − → Ag ( s ), E 0 = 0.80 V
Mg 2+ (1.0 M ) + 2e − → Mg ( s ), E0 = − 2.37 V
+
Applying the diagonal rule, we see that Ag will oxidize Mg :
2+ −
Anode(oxidation): Mg ( s ) → Mg (1.0 M ) + 2e
+ −
Cathode(reduction): 2 Ag (1.0 M ) + 2e → 2 Ag ( s )
+ 2+
Overall Reaction: Mg ( s ) + 2 Ag (1.0 M ) → Mg (1.0 M ) + 2 Ag ( s )
Note that in order to balance the overall equation we multiplied the reduction of
Ag + by 2. We can do because, as an intensive property, E° is not affected by this
procedure. We find the EMF of the cell by using Table 2.1
E 0 cell = E 0 cathode − E 0 anode

= E 0 Ag + / Ag − E 0 Mg2+ /Mg
= 0.80V − ( − 2.37V)
= 3.17V
The positive value of Eocell shows that the forward reaction is favored.
94
Electro chemistry
Experiment 2.4
Determination of Cell Potential of Daniell Cell
Objective:
To determine cell potential of Daniell cell and
To identify the cathode and anode.
Apparatus and chemicals: Voltmeter, copper strip, zinc strip, 1 M ZnSO4 , 1 M
CuSO4 , saturated KCl solution, two 100 mL beakers, U-tube, a fine sandpaper or
file and cotton.
Figure 2.14: Daniell Cell.
95
CHEMISTRY GRADE 12
Procedure:
1. Fill each U-tube with saturated KCl and plug each end with cotton. Be sure not
to trap of any air bubbles in the tube. The cotton also helps to prevent the leak-
age of KCl solution.
2. Clean the metal strips ( Zn and Cu ) with a fine sandpaper or file, if needed.
These strips are to be used as electrodes.
3. Assemble a Zn half-cell as shown in Figure 2. 14a.
4. Dip one end of the Zn metal strip in a 50 mL of 1 M ZnSO4 in a 100 mL bea-
ker. Then, attach one end of the copper wire with the strip of zinc and the other
to terminal of a voltmeter.
5. Do the same thing to construct the copper half-cell shown in Figure 2. 14b. Con-
nect the two half-cells using a salt bridge as shown in Figure 2. 14c.
6. Read the voltage and note the deflection of the voltmeter needle. Record your
observations and give explanations for those observations.
Results and discussion:
1. What does the deflection of needle indicate? Label the cathode and anode.
2. What happens to the needle in the voltmeter when current flows in the external
circuit?
3. Write the half-reactions at each half cells.
4. Is there any color change in the intensity of copper sulphate solution?
Exercise 2.9
1. Can Sn reduce Zn 2+ (aq) under standard-state conditions?
2. What is the standard emf of a galvanic cell made of a Cd electrode in a
1.0 M Cd ( NO3 ) 2 solution and a Cr electrode in a 1.0 M Cr ( NO3 )3 solution
at 25°C?
3. The following overall reaction is Given:
Cu 2+ (1.0 M ) + Mg ( s ) → Cu ( s ) + Mg 2+ (1.0 M )
a. Sketch the Galvanic cell based on the reaction.
b. Identify the cathode and anode.
c. Show the direction of electron flow through the external circuit.
96
Electro chemistry
Electromotive Force (EMF)
Activity 2.12
Form a group. Discuss the following question.
Why does water in a river flow downhill rather than uphill? How do you relate
this concept to the movement of electrons in a wire? After the discussion, share
your ideas with the rest of the class.
Every galvanic or voltaic cell is made up of two half-cells, the oxidation half- cell (anode)
and the reduction half-cell (cathode). One of the electrodes must have a higher electrode
potential (higher tendency to lose electrons) than the other electrode. As a result of this
potential difference, the electrons flow from an electrode at a higher potential to the electrode
at a lower potential. The force which causes the flow of electrons from one electrode to
another electrode and thus results in the flow of current from electrode at higher potential
to electrode at lower potential is called electromotive force (EMF).The EMF of the cell or
cell potential can be calculated from the values of electrode potential of the two half cells
constituting the cell.
1. When oxidation potential of anode and cathode are taken into account
E 0 cell = E 0 anode − E 0 cathode

2. When reduction potential of cathode and anode are taken into account
E 0 cell = E 0 cathode − E 0 anode

Dependence of Cell Potential EMF on Concentration
What is the effect of changing the concentration of reactants on cell potential?
The cell potential depends on the concentrations of ions and on gas pressures. For that
reason, cell potentials provide a way to measure ion concentrations. The pH meter, for
example, depends on the variation of cell potential with hydrogen-ion concentration. You
can relate cell potentials to the standard electrode potentials by using the Nernst. Equation
Nernst Equation
The standard electrode potentials are measured in their standard states when the concentration
of the electrolyte solutions are fixed as 1 M and temperature is 298 K. In actual practice
electrochemical cells do not have always fixed concentration of the electrolyte solutions.
The electrode potentials depend on the concentration of the electrolyte solutions. A change
in concentration affects the change of cell potential which is a result of free energy change.
According to chemical thermodynamics
97
CHEMISTRY GRADE 12
∆G =∆G 0 + RT ln Q
Where, Q is the reaction quotient, and Q was used to calculate the effect of concentration
on ∆G You can apply this equation to a voltaic cell. In that case, the concentrations and
gas pressures are those that exist in the cell at a particular instant.
Since ∆G =−nFEcell and ∆G 0 =

−nFE 0 cell the equation becomes
−nFEcell =
−nFE 0 cell + RT ln Q
This result rearranges to give the Nernst equation that gave a relation between electrode
potentials and the concentration of electrolyte solution
RT 2.303RT
=
Ecell E 0 cell − ln Q or =Ecell E 0 cell − log Q Nernst equation
nF nF
If you substitute 298 K (250C) for the temperature in the Nernst equation and put in
values for Rand F, you get (using common logarithms)
0.0592 RT
=
Ecell E 0 cell − log Q (Value in volts at 25 0C)
nF
You can show from the Nernst equation that the cell potential, Ecell, decreases as the cell
reaction proceeds. As the reaction occurs in the voltaic cell, the concentrations of products
increase and the concentrations of reactants decrease. Therefore, Q and log Q increase.
0.0592 RT
The second term in the Nernst equation, ( log Q) , increases, so that the difference
nF
0.0592 RT
E 0 cell − log Q decreases. Thus, the cell potential, Ecell , becomes smaller.
nF
Eventually the cell potential goes to zero, and the cell reaction comes to equilibrium.
As an example of the computation of the equilibrium constant, consider the following

voltaic cell:
Cd ( s ) | Cd 2+ (0.010 M ) || H + (1.00 M ) | H 2 (1.00 atm) | Pt
The cell reaction is Cd ( s ) + 2 H + (aq )  Cd 2+ (aq ) + H 2 ( g )
and the expression for the equilibrium constant is
Cd 2+  p
  H 2
K=
2
H + 
 
98
Electro chemistry
Note that the hydrogen-gas concentration is given here in terms of the pressure (in
atmospheres). To have consistent units, we convert the given pressure to molarity with the
ideal gas law:
PV = nRT
P n
=
RT V
1 atm
= 0.043M
L atm
0.0821 x 208.15 K
K mol
Then we substitute into the above equation gives as:

0.010 x 0.041
=K = 2
= 4.1 x 10−4
0.00041
(1.00)
Example 2.8
Calculate the equilibrium constant for the following reaction at 25°C
Sn( s ) + 2Cu 2+ (aq )  Sn 2+ (aq ) + 2Cu + (aq )
Solution:
The equilibrium constant (K) can be calculated, using the equation,
nE 0 cell
ln K =
0.0257 V
 nE 0cell 
 
K = e  0.0257 V 
The half-reactions are:

Anode (oxidation): Sn( s ) → Sn 2+ (aq ) + 2e −
Cathode (reduction): 2Cu 2+ (aq ) + 2e − → 2Cu + (aq )
From the above reaction and using Table 2.2, we can calculate the cell potential,
E0 = E0 (cathode) − E 0 (anode)
cell red red
= E0 (Cu 2+ / Cu + ) − E 0 ( Sn 2+ / Sn)
red red
= 0.15 V − (−0.14 V ) = + 0.29 V
E 0 cell is 0.29 V, and n = 2 (because 2 mol of electrons are consumed in the
reaction), then,
nE 0 cell 2 x 0.29 V
=ln k = = 22.6
0.0257 V 0.0257 V
⇒ K = e 22.6 = 6.532 x 109
The reaction favors the formation of products.
99
CHEMISTRY GRADE 12
Example 2.9
Calculate the standard free-energy change for the following reaction at 25°C
2 Au ( s ) + 3Ca 2+ (1.0 M ) → 2 Au 3+ (1.0 M ) + 3Ca ( s )
Solution:
The relationship between the standard free energy change and the
standard cell potential is given by ∆G 0 = −nFE 0 cell . First, let us determine
pK w =− log  H 3O +  − log OH −  =
14
The half-reactions are:
Anode (oxidation): 2 Au ( s ) → 2 Au 3+ (1.0 M ) + 6e −
Cathode (reduction): 3Ca 2+ (1.0 M ) + 6e − → 3Ca ( s )
E0 = E0 (cathode) − E 0 (anode)
cell red red
= E0 (Ca 2+ / Ca ) − E 0 ( Au 2+ / Au )
red red
= −2.87 V − 1.5 V = − 4.37 V
The overall reaction shows that n = 6 (6 moles of electrons are involved). Now
we can calculate ∆G o , using the following equation:
∆G 0 =
− nFE 0 cell
= – 6 × (96500 J/V mol) × (– 4.37 V)
= 2.53 × 106 J/mol = 2.53 × 103 kJ/mol
Therefore, the large positive value of ∆G 0 tells us that the reaction favors the
reactants at equilibrium. The forward reaction is non-spontaneous, that is, gold
cannot reduce calcium.
100
Electro chemistry
Example 2.10
Write the half cell and net cell reactions for the following cell,
Zn | ZnSO4 (aq ) || CuSO4 (aq ) | Cu
Calculate the standard EMF of the given cell
E 0 2+ = − 0.76 V and E 0 2+ = + 0.34 V
Zn / Zn Cu /Cu
Solution: Half-cell reactions
Anode Reaction: Zn → Zn 2+ + 2e−
Cathode Reaction: Cu 2+ + 2e− → Cu
Over all Reaction: Zn + Cu 2+ → Cu + Zn 2+
E0
= E0 − E0
cell cathode anode
=E 0 −E 0
Cu2+ /Cu Zn2+ / Zn
= 0.34 V − (− 0.76
= V ) 1.1 V
Example 2.11
1. What is the cell potential of the following voltaic cell at 250C?
Zn( s ) | Zn 2+ (1.0 x 10−5 M ) || Cu 2+ (0.100 M ) | Cu ( s )
The standard cell potential of this cell is 1.10 V.
Problem Strategy From the cell reaction, deduce the value of n; then calculate K.
Now substitute n, K, and E0cell into the Nernst equation to obtain Ecell.
Solution:
The cell reaction is
Zn( s ) + Cu 2+ (aq )  Zn 2+ (aq ) + Cu ( s )

The number of moles of electrons transferred is two; hence, n = 2. The equilibrium
constant is
 Zn 2+  1.0 x 10−5
K= = = 1.0 x 10−4
Cu 2+
0.100
The standard cell potential is 1.10 V, so the Nernst equation becomes
0.0592
Ecell = E 0 cell − log K
n
0.0592
= 1.10 − log (1.0 x 10−4 )
2
= 1.10 − ( −0.12) = 1.22 V
101
CHEMISTRY GRADE 12
Exercise 2.10
1. In a test of a new reference electrode, a chemist constructs a voltaic
cell consisting of a Zn / Zn 2+ half-cell and an H 2 / H + half-cell under the
following conditions:  Zn 2+  = 0.010 M ,  H +  = 2.5M , pH 2 = 0.30 atm .
Calculate Ecell at 298.15 K.
4. A concentration cell consists of two Ag / Ag 2+ half-cells. In half-cell A, the
electrolyte is 0.010 M
4.
AgNO3 ; in half-cell B, it is 4.0 x 10 ─ 4M AgNO3 . What is the cell potential
at 298.15 K?
5. What is the cell potential of the following voltaic cell at 25C?
5. Zn( s ) | Zn 2+ (0.200 M ) || Ag 2+ (0.002 M ) | Ag ( s )
Concentration Cells
Because electrode potential depends on ion concentrations, it is possible to construct
a galvanic cell from two half-cells composed of the same material but differing in ion
concentrations. Such a cell is called a concentration cell. The two solutions are in separate
half-cells, so they do not mix, but their concentrations become equal as the cell operates.
Finding Ecell for a Concentration Cell
Suppose a voltaic cell has the Cu / Cu 2+ half reaction in both compartments. The cell
reaction is the sum of identical half-reactions, written in opposite directions. The standard
cell potential, E 0 , is zero because the standard electrode potentials are both based
cell
on 1 M Cu 2+ , so they cancel. In a concentration cell, however, the concentrations are
different. Thus, even though E 0 is still zero, the nonstandard cell potential, Ecell ,
cell
depends on the ratio of concentrations, so it is not zero.
For the final concentration to be equal, a concentration cell must have the dilute solution
in the anode compartment and the concentrated solution in the cathode compartment.
For example, let’s use 0.10 M Cu 2+ in the anode half-cell and 1.0M Cu 2+ in the cathode
half-cell (Figure 2. 15):
Anode reaction: Cu ( s ) → Cu 2+ (aq; 0.1 M ) + 2e −
Cu 2+ (aq; 1.0 M ) + 2e − → Cu ( s )
Cathode reaction:
102
Electro chemistry
Figure 2.15. A concentration cell based on the Cu / Cu 2+ half-reaction; Ecell > 0 as

long as the half-cell concentrations are different.
The overall cell reaction is the sum of the half-reactions:
Cu 2+ (aq; 1.0 M ) → Cu 2+ (aq; 0.1 M ) E =?

cell
The cell potential at the initial concentrations of 0.10 M(dilute) and 1.0 M(concentrated),
with n = 2, is obtained from the Nernst equation:
0.0592 V Cu 2+  dilute

=
Ecell E 0
− log
Cu 2+  conc.
cell
2
 0.0592 V 0.10 M 
= 0 V − log 
 2 1.0 M 
 0.0592 V 
=
0 V − (−1.00) 
 2 
= 0.0296 V
 0.0592 V  
Since E 0 is zero, E depends entirely on the   log K  term
cell cell  n  
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CHEMISTRY GRADE 12
How a Concentration Cell Works

• In the anode (dilute) half-cell, Cu atoms in the electrode give up electrons and the
resulting Cu 2+ ions enter the solution and make it more concentrated.
• In the cathode (concentrated) half-cell, Cu 2+ ions gain the electrons and the resulting
Cu atoms plate out on the electrode, which makes that solution less concentrated.
As in any voltaic cell, Ecell decreases until equilibrium is attained, which happens
when Cu 2+  is the same in both half-cells. The same final concentration would
result if we mixed the two solutions, but no electrical work would be done.
Determination of pH
The pH of a solution can be obtained very accurately from cell potential measurements,
using the Nernst equation. To see how this is done, suppose you have a test solution
whose pH you would like to determine. You set up a voltaic cell as follows: You use
the test solution as the electrolyte for a hydrogen electrode and bubble in hydrogen gas
at 1atm. Now connect this hydrogen electrode to a standard zinc electrode to give the
following cell:
Zn( s ) | Zn 2+ (1M ) || H + (test solution) | H 2 (1 atm) | Pt
The cell reaction is: Zn( s ) + 2 H + (test solution) → Zn 2+ (1M ) + H 2 (1 atm)

The cell potential depends on the hydrogen-ion concentration of the test solution,
according to the Nernst equation. The standard cell potential of the cell equals 0.76 V,
and
 Zn 2+  pH 2 1
=K = 2 2
 H +   H + 
Substituting into the Nernst equation, you obtain
0.0592 1
Ecell =
0.76 − log 0.76 + 0.0592 log  H + 
=
+ 2
2  H 
where  H +  is the hydrogen-ion concentration of the test solution.
To obtain the relationship between the cell potential ( Ecell ) and pH , you substitute the
following into the preceding equation? pH = − log  H + 
The result is = Ecell 0.76 − 0.0592 pH Which you can rearrange to give the pH
directly in terms of the cell potential:
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Electro chemistry
0.76 − Ecell
pH =
0.0592
In this way, measurement of the cell potential gives you the pH of the solution.
Exercise 2.11
1. Predict whether the following reaction would proceed spontaneously as
written at 298 K:
Co( s ) + Fe 2+ (aq ) → Co 2+ (aq ) + Fe( s )
=given that Co 2+  =
0.25 M and  Fe 2+  0.94 M
2. A voltaic cell houses the reaction between aqueous bromine and zinc
metal:
Br2 ( s ) + Zn( s ) → Zn 2+ (aq ) + 2 Br − (aq ) E 0 cell =

1.83 V
3. Calculate E 0bro min e , given E 0 Zn = 0.76 V .
Batteries
Activity 2.13
Form a group. Discuss the following questions, and share your idea with
other groups.
1. Collect some used and disposed batteries;
i. classify them as:
a. primary battery or secondary battery.
b. dry cell or alkaline battery etc.
ii. Identify the parts of the batteries, which you have collected.
iii. Describe the type of electrodes as well as physical and chemical nature
of the electrolyte present in each battery.
2. The electrolyte in a discharged lead storage battery freezes at higher
temperature than a fully charged battery. Explain this observation to your
class.
3. Go to a nearby automobile garage and ask the garage mechanic:
a. About the working principle of car battery;
b. how do they come to know whether a car battery needs recharging;
4. Caution! Wear gloves while collecting the disposed batteries.
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CHEMISTRY GRADE 12
A battery is a galvanic cell, or a series of combined galvanic cells, that can be used as a
source of direct electric current at a constant voltage. Although the operation of a battery
is similar in principle to that of the galvanic cells, a battery has the advantage of being
completely self-contained and requiring no auxiliary components such as salt bridges. Here
you will discuss types of batteries that are in widespread use.
Fuel cells
What makes fuel cell different from battery?
A fuel cell is essentially a battery, but it differs in operating with a continuous supply of
energetic reactants, or fuel. Figure 2.16 shows a proton-exchange membrane (PEM) fuel cell
that uses hydrogen and oxygen. In its simplest form, a hydrogen-oxygen fuel cell consists
of an electrolyte solution, such as potassium hydroxide solution, and two inert electrodes.
Hydrogen and oxygen gases are bubbled through the anode and cathode compartments
Figure 2.16: A hydrogen – oxygen fuel cell.
On one side of the cell, the anode, hydrogen passes through a porous material containing a
platinum catalyst, allowing the following reaction to occur:
Anode: H 2 ( g ) → 2 H + (aq ) + 2e −
The 2 H + (aq ) ions then migrate through a proton-exchange membrane to the other side of
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Electro chemistry
the cell to participate in the cathode reaction with O2 ( g )
Cathode: O2 ( g ) + 2 H + (aq ) + 4e − → H 2O( g )
The sum of the half-reactions is
Anode : 2 H 2 ( g ) + 4OH − (aq ) → 4 H 2O(l ) + 4e −
Cathode : O2 ( g ) + 2 H 2O(l ) + 4e − → 4OH − (aq )
Overall : 2 H 2 ( g ) + O2 ( g ) → 2 H 2O(1)
which is the net reaction in the fuel cell. The first applications of PEM fuel cells were
in space, but more recently, they have provided power for lighting, emergency power
generators, communications equipment, automobiles, and buses. Other types of cells
using other materials and fuels such as hydrocarbons or methanol are either in commercial
production or under development.
Exercise 2.12
1. Explain the difference between a dry cell and a lead storage battery.
2. Write the reactions that occur at the cathode and anode during the
charging of a lead storage battery.
3. a. What is the electrolyte in a dry cell?
b. Write the half-reactions for the reducing and oxidizing agents in a dry
cell.
Corrosion of Metals
What are the causes of corrosion?
Corrosion is the term usually applied to the deterioration of metals by an electrochemical

process..corrosion causes tens of billions of dollars of damage to cars, ships, buildings, and
bridges each year. This natural process, which oxidizes metals to their oxides and sulfdes,
shares similarities with the operation of a voltaic cell. We focus on the corrosion of iron, but
many other metals, such as copper and silver, also corrode.
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CHEMISTRY GRADE 12
The Corrosion of Iron
What is the economic disadvantage of iron corrosion?
The most common and economically destructive form of corrosion is the rusting of iron.
Iron rust is not a direct product of the reaction between iron and oxygen but arises through
a complex electrochemical process. The important facts about iron corrosion are:
 Iron does not rust in dry air; moisture must be present.

 Iron does not rust in air-free water; oxygen must be present.
 Iron loss and rust formation occur at different places on the same object.
 Iron rusts more quickly at low pH (high  H +  ).

 Iron rusts more quickly in ionic solutions
 Iron rusts more quickly in contact with a less active metal (such as Cu ) and more
slowly in contact with a more active metal (such as Zn )
Two separate Redox processes occur during corrosion:
1. The loss of iron. A strain or dent in contact with water is usually the site of iron loss. This
site is called an anodic region because of the following half-reaction (Figure 2.17):
Anodic region; Oxidation : Fe( s ) → Fe 2+ (aq ) + 2e −
Figure 2.17A small area of the surface, showing the steps in the corrosion process.
Once the iron atoms lose electrons, the damage to the object has been done, and a pit
(depression or hollow) form where the iron is lost. The electrons given up by iron reduce
atmospheric oxygen to water at the cathode, which is another region of the same metal’s
surface:
Cathodic region; r e duction : O2 ( g ) + 4 H + (aq ) + 4e − → 2 H 2O
108
Electro chemistry
This portion of the corrosion process (the sum of these two half-reactions) occurs without
any rust forming:
Overall reaction : 2 Fe( s ) + O2 ( g ) + 4 H + (aq ) → 2 Fe 2+ (aq ) + 2 H 2O(l )
2. The rusting process. Rust forms in another redox reaction. The Fe 2+ ions formed at the
anodic region disperse through the water and react with O2 , often away from the pit, to
form the Fe3+ in rust. The overall reaction for this step is:
1
2 Fe 2+ (aq ) + O2 ( g ) + (2 + n) H 2O(l ) → Fe2O3 .nH 2O( s ) + 4 H + (aq )
2
[The coefficient n for H 2O appears because of rust, Fe2O3 .nH 2O , has a variable number of
waters of hydration.] The rust deposit is incidental to the real damage, which is the loss of
iron that weakens the strength of the object. Adding the two previous equations gives the
overall equation for the loss and rusting of iron:
3
Fe( s ) + O2 ( g ) + nH 2O(l ) → Fe2O3 .nH 2O( s )
2
Other species ( 2Fe 2+ and 2H 2O ) also cancel, but we showed the canceled  H +  ions to
emphasize that they act as a catalyst: they speed the process as they are used up in one step
and created in another. For this reason, rusting is faster at low pH (high  H +  ).
Ionic solutions speed rusting by improving the conductivity of the aqueous medium near
the anodic and cathodic regions. The effect of ions is especially evident on ocean going
vessels and, on the underbodies, and around the wheel wells of cars driven in cold climates,
where salts are used to melt ice on slippery roads. Thus, in some key ways, corrosion
resembles the operation of a voltaic cell:
• Anodic and cathodic regions are physically separated.

• The regions are connected via an external circuit through which the electrons travel.
• In the anodic region, iron behaves like an active electrode, whereas in the cathodic
region, it is inactive.
• The moisture surrounding the pit functions somewhat like an electrolyte and salt
bridge.
Metallic corrosion is not limited to iron. Consider aluminum, a metal used to make many
useful things, including airplanes and beverage cans. Aluminum has a much greater tendency
to oxidize than iron does; in Table 2.2 we see that Al has a more negative standard reduction
potential than Fe . Based on this fact alone, we might expect to see airplanes slowly corrode
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CHEMISTRY GRADE 12
away in rainstorms, and soda cans transformed into piles of corroded aluminum. These
processes do not occur because the layer of insoluble aluminum oxide ( Al2O3 ) that forms
on its surface when the metal is exposed to air serves to protect the aluminum underneath
from further corrosion. The rust that forms on the surface of iron, however, is too porous
to protect the underlying metal. Coinage metals such as copper and silver also corrode, but
much more slowly.
Cu ( s ) → Cu 2+ (aq ) + 2e −
Ag ( s ) → Ag + (aq ) + 2e −
In normal atmospheric exposure, copper forms a layer of copper carbonate ( CuCO3

), a green substance also called patina, that protects the metal underneath from further
corrosion. Likewise, silverware that comes into contact with foodstuffs develops a layer of
silver sulfide ( Ag 2 S ).
Exercise 2.13
1. Define corrosion.
2. Explain the negative effects of corrosion.
3. Aluminum does not rust as iron does. Why?
Protecting Against the Corrosion of Iron
Activity 2.14
Form a group and discuss each of the following questions. After the
discussion, share your ideas with the other groups.
1. List the methods that help to prevent the rusting of iron.
2. What is common in all methods of preventing the rusting of iron?
A number of methods have been devised to protect metals from corrosion. Most of these
methods are aimed at preventing rust formation. The most obvious approach is to coat the
metal surface with paint. However, if the paint is scratched, pitted, or dented to expose even
the smallest area of bare metal, rust will form under the paint layer.
The tendency for iron to oxidize is greatly reduced when it is alloyed with certain other
metals. For example, in stainless steel, an alloy of iron and chromium, a layer of chromium
oxide forms that protects the iron from corrosion. An iron container can be covered with
a layer of another metal such as tin or zinc. The point regarding corrosion concerns the
110
Electro chemistry
relative activity of other metals in contact with iron. The essential idea is that iron functions
as both anode and cathode in the rusting process, but it is lost only at the anode. Thus
1. Corrosion increases when iron behaves more like the anode. When iron is in contact
with a less active metal (weaker reducing agent), such as copper, it loses electrons more
readily (its anodic function is enhanced; Figure 2. 18). Non conducting rubber or plastic
spacers are placed between the metals to avoid this problem.
Figure2.18: The effect of Metal-metal contact on the corrosion of iron; Fe in contact

with Cu corrodes faster.
2. Corrosion decreases when iron behaves more like the cathode. In cathodic protection,
the most effective way to prevent corrosion, iron makes contact with a more active metal
(stronger reducing agent), such as zinc. The iron becomes the cathode and remains
intact, while the zinc acts as the anode and loses electrons (Figure 2. 19). Coating iron
with a “sacrificial” layer of zinc is called galvanizing. In addition to blocking physical
contact with H 2O and O2 , the zinc (or other active metal) is “sacrificed” (oxidized)
instead of the iron. Sacrificial anodes are used underwater and underground to protect
iron and steel pipes, tanks, oil rigs, and so on.
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CHEMISTRY GRADE 12
Figure 2. 19: The effect of Metal-metal contact on the corrosion of iron; Fe in contact
with Zn does not corrode. This method of preventing corrosion is known as cathodic
protection
Unit Summary
~ An oxidation-reduction (redox) reaction involves the transfer of electrons from

a reducing agent to an oxidizing agent.
~ The half-reaction method of balancing divides the overall reaction into half
reactions that are balanced separately and then recombined.
~ There are two types of electrochemical cells: voltaic and electrolytic cell. In a
voltaic cell, a spontaneous reaction generates electricity and does work on the
surroundings. In an electrolytic cell, the surroundings supply electricity that
does work to drive a non-spontaneous reaction.
~ In both types of cells, two electrodes dip into electrolyte solutions; oxidation
occurs at the anode, and reduction occurs at the cathode.
~ A voltaic cell consists of oxidation (anode) and reduction (cathode) half-cells,
connected by a wire to conduct electrons and a salt bridge to maintain charge
neutrality.
~ Electrons move from the anode (left) to the cathode (right), while cations move
from the salt bridge into the cathode half-cell and anions move from the salt
bridge into the anode half-cell.
~ The cell notation shows the species and their phases in each half-cell, as well as
the direction of current flow.
~ The output of a cell is the cell potential ( Ecell ), measured in volts (1V = 1J/C).
112
Electro chemistry
~ With all substances in their standard states, the output is the standard cell
potential ( E 0 cell ).
~ E cell > 0 for a spontaneous reaction at standard-state conditions.

0
~ By convention, a standard electrode potential ( E 0 half − cell ) refers to the

reduction half reaction.
0
E0 E0
~ E cell equals half − cell of the cathode minus half − cell of the anode.
~ Using a standard hydrogen (reference) electrode ( E 0 half − cell = 0V ), E 0 half − cell
values can be measured and used to rank oxidizing (or reducing) agents.
~ Spontaneous redox reactions combine stronger oxidizing and reducing agents
to form weaker reducing and oxidizing agents, respectively.
~ A metal can reduce another species ( H + , H 2O , or an ion of another metal) if

E 0 cell for the overall reaction is positive.
~ A spontaneous process has a negative ∆G and a positive Ecell , ∆G = −nFE

. The ∆G of the cell reaction represents the maximum electrical work the cell
can do.
~ The standard free energy change, ∆G 0 , is related to E 0 cell and to K .
~ For nonstandard conditions, the Nernst equation shows that Ecell depends on
E 0 cell and a correction term based on Q . Ecell is high when Q is small (high
[reactant]), and it decreases as the cell operates. At equilibrium, ∆G and Ecell
are zero, which means that Q = K
~ Concentration cells have identical half-reactions, but solutions of differing
concentration. They generate electrical energy as the concentrations become
equal.
~ Ion-specific electrodes, such as the pH electrode, measure the concentration

of one species.
~ Batteries are voltaic cells arranged in series and are classified as primary (e.g.,
alkaline, mercury, and silver), secondary (e.g., lead-acid, nickel metal hydride,
and lithium-ion), or fuel cells.
~ Supplying electricity to a rechargeable (secondary) battery reverses the redox
reaction, re-forming reactant.
~ Fuel cells are not self-contained and generate a current through the controlled
oxidation of a fuel such as H 2 .
~ Corrosion damages metal structures through a natural electrochemical process.
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CHEMISTRY GRADE 12
~ Iron corrosion occurs in the presence of oxygen and moisture and is increased
by high  H +  , high [ion ] , or contact with a less active metal, such as Cu .

2+
~ Fe is oxidized and O2 is reduced in one redox reaction, while Fe is
oxidized and O2 is reduced to form rust (hydrated form of Fe2O3 ) in another
redox reaction that often takes place at a different location.
~ Because Fe functions as both anode and cathode in the corrosion process, an
iron object can be protected by physically covering it or by joining it to a more
active metal (such as Zn , Mg , or Al ), which acts as the anode in place of the
Fe .
~ An electrolytic cell uses electrical energy to drive a non-spontaneous reaction.
~ Oxidation occurs at the anode and reduction at the cathode, but the direction
of electron flow and the charges of the electrodes are opposite those in voltaic
cells.
~ In electrolysis of a pure molten salt, the metal cation is reduced at the cathode,
and the nonmetal anion is oxidized at the anode.
~ The reduction or oxidation of water takes place at nonstandard conditions.
~ Overvoltage causes the actual voltage required to be unexpectedly high
(especially for gases, such as H 2 and O2 ) and can affect the product that forms
at each electrode
~ The amount of product that forms depend on the quantity of charge flowing
through the cell, which is related to the time the charge flows and the current.
 Anion  Electrolysis  Primary batteries

 Anode  Electrolyte  Redox reaction
 Battery  Electrolytic cell  Reducing agent
 Brine solution  Electroplating  Reduction
 Cathode  Faraday’s first law  Salt bridge
 Cation  Faraday’s second law  Secondary batteries
 Cell notation  Galv  SHE
 Concentrated solution  Galvanic Cell / Voltaic  Standard electrode
 Conductivity Cell potential
 Corrosion  Nernst equation
 Daniell cell  Oxidation
 Dilute solution  Oxidation number
 Dry cell  Oxidizing agent
 Electrochemical series  Preferential discharge
114
Electro chemistry
REVIEW EXERCISE ON UNIT 2

Part I: Multiple Choice Questions
1. What is the oxidation number of chromium in the ionic compound ammonium

dichromate? (NH4)2Cr2O7?
a. + 3 c. + 5
b. + 4 d. + 6
2. What are the oxidation numbers for nickel, sulfur, and oxygen in Ni2(SO4)3?
a. Ni +3; S +6; O -2 c. Ni +3; S +4; O -2
b. Ni +2; S +4; O -2 d. Ni +2; S +2; O -2
3. What is the coefficient for hydroxide, and how many electrons are transferred after
balancing the reaction? Pb(OH ) 4 2− + ClO − → PbO2 + Cl − + OH − + H 2O

a. 2 OH─ and 2 electrons c. 1 OH─ and 2 electrons
b. 3 OH─ and 4 electrons d. 2 OH─ and 4 electrons
4. What was oxidized and what was reduced in the following reaction?
2 Hg 2+ + N 2 H 4 → 2 Hg + N 2 + 4 H +
a. Hg2+ was oxidized; N2H4 was reduced

b. Hg2+ was reduced; N2H4 was oxidized
c. Hg2+ was oxidized; N2H4 was oxidized
d. Hg2+ was reduced; N2H4 was reduced
5. Which of the following statements is true about electrochemical cells?
a. Reduction occurs at the anode
b. An element with a high affinity for electrons is likely to be easily oxidized
c. Oxidation occurs at the anode
d. Only oxidation half–reactions are useful
6. Which statement regarding voltaic cells is not correct?
a. Reduction occurs at the cathode.
b. Anions move through the barrier/bridge toward the electrode where oxidation
is occurring.
c. The electrode where reduction is occurring is represented by a positive sign
d. Electrons flow in the external circuit from the cathode to the anode.
7. The electrochemical reaction shown below is Given, if the standard reduction
potential of Zn2+--> Zn is – 0.76 V, what is the standard reduction potential of
Mg 2+ → Mg ? Mg | Mg 2+ (aq ) || Zn 2+ (aq ) | Zn E˚ = + 1.61 V

a. – 0.85 V c. + 2.37 V
b. + 0.85 V d. – 2.37 V
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CHEMISTRY GRADE 12
8. Use the Table of Standard Reduction Potential stable, which species would react with
Al3+?
a. Pb only c. Fe and Pb
3+
b. Au only d. Both Mg and K
9. The oxidation of hydrogen by oxygen is one of the most-used reactions in fuel-cell
technology. The overall reaction, which is given below, has a ΔG° value of – 474 k
J/mol. What is the standard cell potential for this fuel cell?
2 H 2 ( g ) + O2 ( g ) → 2 H 2O(l ) ΔG° = – 474 kJ/mol
a. 2.46 V c. 1.23 V
b. 4.91 V d. 2.46 V
10. Which one of the following equations shows the relationship between standard Gibbs
free energy and equilibrium constant?
a. K= ∆G0 c. ∆G0 = – RT ln K
b. K = RT ln ∆Go d. ∆G0 = RT ln K
11. 11. What is ΔG° for the following balanced reaction, if E˚ = + 2.431 V?
Al ( s ) + Fe 2+ (aq ) → Al 3+ + Fe(l ) E˚ = + 2.431 V
a. -704 kJ/mol c. -235 kJ/mol

b. +704 kJ/mol d. -469 kJ/mol
12. 12. The value of E˚ for the following reaction is 1.10 V. What is the value of Ecell when
the concentration of Cu2+ is 1.0 M and the concentration of Zn2+ is 0.025 M?
Zn( s ) + Cu 2+ (aq ) → Cu ( s ) + Zn 2+ (aq ) E˚ =1.10 V, Cu 2+  = 1.0 M and
 Zn 2+  = 0.025M
a. 1.40 V c. 1.15 V
b. 0.95 V d. 0.80 V
13. 13. One of the basic differences between a fuel cell and a battery is:
a. a fuel cell is rechargeable, while a battery is not.
b. a fuel cell does not store chemical energy, but a battery can store chemical
energy.
c. both a fuel cell and a battery are rechargeable.
d. a and c.
14. 14. A battery is ‘‘dead’’ if:
a. reactants and products reach their equilibrium concentrations.
b. Ecell is equal to zero.
c. ΔG is equal to zero.
d. all of the above.
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Electro chemistry
15. A metal corrodes if:

a. it serves as cathode in the corrosion process.
b. it serves as anode in the corrosion process.
c. it does not react with oxygen.
d. all of the above.
1. Define each of the following terms:

a. oxidation d. electrolytic cell
b. reduction e. corrosion
c. Galvanic cell
2. Balance each of the following chemical equations, using oxidation state change
method.
a. 2 Al ( s ) + 3H 2 SO4 (aq ) → Al2 ( SO4 )3 (aq ) + 3H 2 ( g )
b. Cu + HNO3 → Cu ( NO3 ) 2 + NO2 + H 2O

3. Balance each of the following chemical equations in basic and acidic medium, using
ion-electron method.
− 2− −
a. ClOü + SO → SO + Cl
b. H S + NO − → S + NO
2 3 8
c. H 2 S + HNO3 → NO + S + H 2O
d. Cu + SO 2− → Cu 2+ + SO
4 2
4. When an aqueous solution of copper(II)sulfate, CuSO4, is electrolyzed, copper metal
is deposited.
Cu 2+ + 2e − → Cu ( s )
(The other electrode reaction gives oxygen: ( 2 H 2O → O2 + 4 H + + 4e − ) If a constant

current was passed for 5.00 h and 404 mg of copper metal was deposited, what was
the current?
5. When an aqueous solution of potassium iodide is electrolyzed using
platinum electrodes, the half-reactions are: 2 I − (aq ) → I 2 (aq ) + 2e − and
2 H 2O(l ) + 2e − → H 2 (aq ) + 2OH − (aq )

How many grams of iodine are produced when a current of 8.52 mA flows
through the cell for 10.0 min?
6. Predict whether the following reaction would proceed spontaneously as written at
298 K:
117
CHEMISTRY GRADE 12
Co( s ) + Fe 2+ (aq ) → Co 2+ (aq ) + Fe( s ) , given that [Co2+] = 0.25 M and [Fe2+] = 0.94
M.
7. What is ΔG0at 10000C for the following reaction? CaCO3 ( s )  CaO( s ) + CO2 ( g )
8. Is this reaction spontaneous at 1000 0C and 1 atm?
9. Using standard electrode potentials, calculate the standard free-energy change at 25C
for the reaction
Zn( s ) + 2 Ag + (aq ) → Zn 2+ (aq ) + 2 Ag ( s )

10. The standard cell potential for the following voltaic cell is 1.10 V:
Zn( s ) | Zn 2+ (aq ) || Cu 2+ (aq ) | Cu ( s )
Calculate the equilibrium constant Kc for the reaction:
Zn( s ) + Cu 2+ (aq )  Zn 2+ (aq ) + Cu ( s )

11. Explain a. How corrosion occurs? b. How can corrosion be prevented?
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Industrial Chemistry
UNIT
INDUSTRIAL CHEMISTRY
3
Unit outcomes
At the end this unit, students will be able to

 list the renewable and non-renewable natural resources and appreciate
their importance to industry as raw materials
 describe the relationship between natural resources and
industry
 list some chemical and related industries in Ethiopia
 list some important chemicals used for the manufacture of valuable
products
 explain the major steps in the industrial production of ammonia,
nitric acid, sulphuric acid, sodium hydroxide, sodium carbonate and
aluminum sulphate and di-ammonium phosphate and other Nitrogen
fertilizers; and
 list some important direct uses of NH3, HNO3, H2SO4, Na2CO3 and their
uses as raw material in production of other products
 list some important uses of NH3, HNO3, H2SO4, and Na2CO3 as raw
material in production of other products.
 list some important uses of DAP, (NH4)2HPO4, nitrogen fertilizers,
insecticides and Herbicides
 prepare insecticides from locally available material
 describe the uses of the common insecticides and pesticides that are
manufactured in chemical industries
 discuss the important steps in the production of glass, ceramics, cement,
sugar and paper and pulp
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CHEMISTRY GRADE 12
 describe the important steps in the production of soaps and detergent,

and beverage prepare soaps in small scale from the available
resources
 describe the tanning process
 apply local methods of tanning
 use local methods of food preservation
 develop enquiry skills along this unit: observing, predicting, classifying,
communicating and inferring
Start-up activity
From your grade 10 lesson, you have learnt about the occurrence and
extraction of some important metals and non-metals. Thus, in small groups
discuss and present to the class the occurrence and important of some metals
and non-metal’s that are used as a raw material for the production of desired
products.
3.1 Introduction
At the end of this section, students will be able to:
 define industrial chemistry
 list general characteristics of chemical industries;
 mention the role of industrial chemistry for the society
Activity 3.1
1. Discuss in groups of three and comment the following statement “It is
very difficult to think life without chemical industry.”
2. List five products that are manufactured by Ethiopian chemical industries.
Report your answer to your classmates.
The 19th century industrial revolution resulted the beginning of the development of chemi-
cal industries at a very high rate. Following this, the demands for goods produced through
chemical processes increased. Today chemical industries in both developed and developing
countries produce a number of very useful products. This includes synthetic fibers, plastics,
rubber fertilizers, dyes, drugs and many other products.
Chemistry and chemical technology are very important for economic growth and devel-
opment of especially for developing country like Ethiopia. Ethiopia has minerals (metal
ores) deposits which are sources of iron, lead, copper, gold, platinum, tantalum and many
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Introduction
rare-earth metals. Moreover, rock salt gypsum, coal, and crude oil are found. So, Ethiopia
needs industrial revolution to use its mineral deposits to produce various chemicals in large
scale.
So, in this context what meant by industrial Chemistry?
Industrial chemistry is a branch of chemistry which applies physical and chemical proce-
dures towards the transformation of natural raw materials and their derivatives to products
that have beneficial to humanity.
Industrial chemistry differs from the classical chemistry in that it closes the gap created
in concepts between chemistry as it is taught in schools, and chemistry as it is practiced
commercially.
Industrial chemistry is the basis of chemical industry. Chemical industry is an institution

involved in the production of chemical products such as food, medicine, building materials,
plastics, etc. The chemical industry involves the use of chemical processes such as chem-
ical reactions and refining methods to produce a wide variety of materials with desirable
properties and quality to satisfy social needs. Most of these products, in turn, can be used by
other chemical industries to manufacture other items or can be used directly by consumers.
Generally, chemical industries
• use naturally-available raw materials to produce the desired products.
• involve chemical reactions to transform raw materials into finished and semi-finishe
products.
• consume relatively large quantities of energy during the manufacturing process.
• use safe operation methods in their manufacturing processes, and
• test their products during and after manufacture in their quality control laboratories
to ensure that the products meet the required specifications.
Exercise 3.1
1. Define “industrial chemistry?
2. Discuss how chemical industries are considered to be the prominent one
when dealing with manufacturing industries.
3. List the characteristics of chemical industries.
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CHEMISTRY GRADE 12
3.2 Natural Resources and Industry

At the end of this section, you will be able to:
 define natural resources
 list the types of natural resources
 classify chemical industries based on the raw materials they use to
manufacture their products
 Classify chemical industries based on the type of product they
manufactured
 describe the applications of minerals in industry.
Activity 3.2
Discuss the following questions in groups and present your findings to your
classmates.
1. How can animals and plants be replaced once they die?
2. What are fossil fuels?
3. Can fossil fuels be renewed?
4. Explain the importance of natural resources for chemical industries using
examples?
3.2.1 Natural resources (Raw materials)
Natural resources are the raw materials for the chemical industry which are obtained from
the natural environment. The raw materials are obtained from the different components of
the natural environment. These are listed below
 From the atmosphere: The earth’s atmosphere has approximately 5x 1015 tons of
gases. It is composed of different gases including namely N2 , O2 , Ne, Ar, Kr and
Xe. They are important industrial raw materials. Thus, the natural supply of these
gases is unlimited.
 From the hydrosphere: Ocean water which amounts to about 1.5x 1021 liters con-
tains about 3.5 percent by mass dissolved material. Seawater is a good source of
sodium chloride, magnesium and bromine.
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Natural Resources and Industry
 From the lithosphere: The vast majority of elements are obtained from the earth’s
crust in the form of mineral ores, carbon and hydrocarbons. Coal, natural gas and
crude petroleum besides being energy sources are also converted to thousands of
chemicals.
 From the biosphere: Vegetation and animals contribute raw materials to the so-called
agro-based industries. Oils, fats, waxes, resins, sugar, natural fibres and leather are
examples of thousands of natural products.
Classification of Natural Resources

Natural resources can be classified as renewable and non-renewable resources.
Renewable resources: The resources that can be replenished through rapid natural cycles
are known as renewable resource. These resources are able to increase their abundance
through reproduction and utilization of simple substances. Examples of renewable resourc-
es are plants, (crops and forests), and animals which are being replaced from time to time
because they have the power of reproducing and maintain life cycles. There are also re-
newable resources without any life cycle. These include wood and wood-products, natural
rubber, fibers (e.g. cotton, jute, and animal wool, silk and synthetic fibers), pulp products,
leather. Furthermore, resources, water and soil are also classified as renewable resources.
Moreover, solar energy is considered as a renewable resource in as much as solar stocks are
inexhaustible on the human scale.
Non-Renewable Resources: The resources that cannot be replenished (regenerated)

through natural processes are known as non-renewable resources. These are available in
limited amounts and cannot be increased. These resources include fossil fuels (petrol, coal
etc.), metals (iron, copper, gold, silver, lead, zinc etc.), minerals and salts (carbonates, phos-
phates, nitrates etc.). Once a non-renewable resource is consumed, it is gone forever. Thus,
a substitute for it is necessary.
3.2.2 Industry
Industry is a well-organized facility with a high degree of automation and specialization

where large-scale manufacturing of goods take place. Nevertheless, it can also include oth-
er commercial activities that provide goods and services such as agriculture, transportation,
hospitality, and many others.
Manufacturing industry: Manufacturing industry is a compartment of industry or econ-

omy which is concerned with the production or making of goods out of raw materials by
means of a system of organized labor.
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CHEMISTRY GRADE 12
Classification of manufacturing industry

Manufacturing industries use different type of raw materials, skills, and technologies. As a
result, different types of products are manufactured.
Chemical Industry: Chemical industry is a facility where industrial chemicals are manu-
factured. The products result from:
a) Chemical reaction between organic materials, or inorganic materials, or both

b) Extraction, separation, or purification of natural products, with or without the aid of
chemical reactions
c) The preparation of specifically valuable materials
Classification of the chemical industry based on raw material used for production
1. Chemical industries using natural raw materials (resources) For example: Sugar
industries use sugar cane to manufacture sugar.
2. Chemical industries using products from other industries to manufacture their prod-
ucts. For example: Detergent and soap manufacturing industries use preprocessed
products like caustic soda, caustic potash and related compounds to manufacture
their products.
Classification based on the product type
Examples are:
• Food,
• beverages
• Textiles,
• wearing apparel,
• leather goods industries
• Paper products, Chemical etc.
Exercise 3.2
1. List the types of manufacturing industries based on their products.
2. Give examples of renewable and non-renewable natural resources
124
Manufacturing of valuable products/ Chemicals
3.3 Manufacturing of valuable products/

Chemicals
At the end of this section, you will be able to
 describe the meaning of “manufacturing of valuable products in
industries”.
 list and describe the important steps for the production of NH3 in Haber
process
 explain the conditions required to increase the production of NH3 in
Haber process
 list some important direct uses of H2SO4 and its uses as raw material in
production of other products
 list the physical and chemical properties of HNO3
 describe the important steps for the production of HNO3 in Ostwald
Process
 list the physical and chemical properties of H2SO4
 explain how the production of H2SO4 is considered as the vital to
measure the development of a Nation
 draw the schematic diagram which shows the steps followed in the
production of H2SO4 in contact process
 list some important direct uses of H2SO4 and its uses as raw material in
production of other products
 list the physical and chemical properties of Na2CO3
 state the raw material used to manufacture Na2CO3
 draw the schematic diagram which shows the steps followed in
production of Na2CO3 in Solvay process
 list some important direct uses of Na2CO3 and its uses as raw material
in production of other products
 discuss the uses of DAP, (NH4 )2 HPO4 , Nitrogen fertilizers, herbicides
and insecticides in the agriculture sector
 apply ingenious knowledge to produce natural compost
 use local resources to prepare insecticides
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CHEMISTRY GRADE 12
Manufacturing of some valuable products: Manufacturing of valuable products involve

a number of chemical processes. The process is designed to produce a desired product from
a variety of starting raw materials using energy through a succession of treatment steps
integrated in a rational fashion (Figure 3.1). The treatments steps could be either physical
or chemical in nature.
Figure 3.1: Basic steps in a manufacturing process.
Valuable products include every industrial product. These products are either directly used
or serve as raw materials to synthesize products that are important to solve the society de-
mands in different necessities. Both organic and inorganic chemicals could be used in the
manufacturing process.
3.3.1 Production of Ammonia (NH3)
Activity 3.3
Discuss in group and present your answer to the class.
1. Why ammonia is highly soluble in water?
2. List and describe the conditions that are required to get high yield of
ammonia using Le Chatelier’s principle?
Properties
Ammonia is lighter than air with a density of 0.769 kg/m3 at STP. Ammonia is commer-
cially and commonly available as an aqueous solution; the most common commercial for-
mulation is 28–30% NH3. In the aqueous solution ammonia is partially ionized according
to the equilibrium:
NH 3 + H 2 O ⇔ NH 4+ + OH −
and it is often referred to as ammonium hydroxide. It is a weak base. It is colorless with

sharp and intensely irritating gas at room temperature. Its melting point is -77.7. Its boiling
point is -33.35. Its solubility in water at 25 is 34% (w/w).
Uses
126
Ammonia is an important compound, essential to man for a variety of diverse uses. It is

used as a cleaning agent, antimicrobial agent, a raw material for the production of nitrogen
fertilizers, raw material in the manufacturing of explosives such as nitrocellulose and TNT,
used in the production of soda ash and in the Ostwald process to get nitric acid etc. Such a
diverse applicability has caused large demand for its production.
Preparation
Ammonia is easily made in the laboratory by heating an ammonium salt, such as ammoni-
um chloride NH4Cl with a strong alkali, such as sodium hydroxide or calcium hydroxide.
2 NH 4Cl + Ca ( OH )2 → CaCl2 + 2 H 2O + 2 NH 3 ( g )
The gas may also be made by warming concentrated ammonium hydroxide. However, its
diverse applicability has caused large demand for its production. The development of the
Haber-Bosch process for ammonia production has made it possible to meet this demand.
So, the principal commercial method of production of ammonia is the Haber process, the
direct combination of nitrogen and hydrogen under high pressure in the presence of a cat-
alyst.
The Haber process was found by the German chemist, Fritz Haber, in the early 20th centu-
ry. It involved the practical use of atmospheric hydrogen and nitrogen to produce ammonia.
Carl Bosch was tasked with scaling up the process to an industrial production. The efforts
of both these men were recognized in the form of Nobel prizes that were awarded to them
in 1918 and 1931, respectively. This also led to the process being called the Haber-Bosch
process. Presently, about 454 million tons of nitrogen fertilizers are produced using the
Haber-Bosch process. They are extensively used to increase crop yields.
Steps Involved in Ammonia Production

Step 1: The primary requirements for the production of ammonia are hydrogen (H2) and
nitrogen (N2). H2 was initially obtained by electrolyzing water, thus, splitting the
water molecule into its components – hydrogen and oxygen. In recent times, this
method has been replaced by the use of methane as a source. Methane is easily
acquired from natural gas, and requires very less external energy to produce hydro-
gen. The other substrate, nitrogen, is obtained by carrying out fractional distillation
of air.
Step 2: The hydrogen and nitrogen are then, introduced into a chamber containing iron par-
ticles or lined internally with iron, and a pressure of 15 – 25 MPa at a temperature
of 300 – 500 °C is applied to the gases. These conditions cause the gases to react
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CHEMISTRY GRADE 12
and produce ammonia, and the following reaction occurs:
N 2 + 3H 2 → 2 NH 3
Due to the Le Chatelier’s principle of chemical equilibrium, there would be a continuous

decline in the yield as the reaction progresses. High pressure conditions are applied to over-
come this effect. In addition, a high temperature conditions are required during the produc-
tion of ammonia. Why high temperature conditions are required? The reaction involved in
the production of NH3 occurs as follows:
N → N
2( g ) 2( adosbed )
N → 2N
2( adosrbed ) ( adsorbed )
H → H
2( g ) 2( adosbed )
H → 2H
2( adosrbed ) ( adsorbed )
N + 3H → NH
2( adsobed ) 2( adsorbed ) 3( adsorbed )
Step 3: The hot mixture of gases is then passed through a condenser. Since ammonia con-
denses easily as compared to nitrogen and hydrogen, the liquefied ammonia is
collected and removed, and the leftover nitrogen and hydrogen gases are re-intro-
duced into the reactor. Thus, pressure is maintained, and there is no loss or wastage
of reactants. This recycling of the raw materials allows a 97% conversion of initial
reactants into ammonia, which is, then, used to produce a variety of products. The
steps are shown in Figure 3.2.
Leftover H2 + N2
Coolant
H2 + N2
NH3 ammonia
Condesner
Catalyst Reactor
Figure 3.2: production of NH3 using Haber-Bosh process
128
Experiment 3.1
Preparation and Testing of Ammonia
Objective: In this experiment, students prepare ammonia, investigate its solubility in
water and test its alkaline nature
Equipment Apparatus
Eye protection Retort stand, boss and clamp Boiling tube with stopper and delivery
tube (see diagram below) – this apparatus must be dry Boiling tubes, x2 – must be
thoroughly dry Beaker, 100 cm Beaker, 250 cm or larger Bunsen burner Heat resistant
mat Spatula.
Chemicals
Ammonium chloride (HARMFUL) Calcium hydroxide (IRRITANT) Calcium oxide
(CORROSIVE) – optional Concentrated hydrochloric acid (CORROSIVE) Red lit-
mus paper Blue litmus paper Universal indicator paper.
Safety Precautions
Wear eye protection throughout. Ammonia gas is TOXIC and DANGEROUS FOR
THE ENVIRONMENT and pungent-smelling and must not be inhaled. The experi-
ments must only be carried out in a fume cupboard or in a well-ventilated laboratory.
Procedure
1. In a small beaker, mix 2 spatulas of the ammonium chloride with 2 spatulas of the
calcium hydroxide together. The two solids begin to react immediately on mixing.
2. Hold a piece of each color of litmus paper over the mixture and observe the color
change. Test also with a piece of universal indicator paper.
3. Transfer the mixture of ammonium chloride and calcium hydroxide into a boiling
tube and set up the apparatus as shown in the diagram.
Ammonium chloride
and calcium hydroxide
Delivery tube
Boiling tube
Figure 3.3: The equipment required for producing ammonia gas

4. Optional: put the lump of calcium oxide into the boiling tube containing the am-
monium chloride/calcium hydroxide mixture. The calcium oxide will absorb the
water produced in the reaction and ensure that the ammonia gas is dry.
5. Gently warm the reaction mixture.
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CHEMISTRY GRADE 12
6. Collect a test tube which contains a few drops of concentrated hydrochloric acid.
Remove the stopper from this test tube and hold the open end near the end of the
ammonia gas delivery tube. Observe what happens. Replace the stopper on the
test tube of hydrochloric acid and return the test tube to its original place.
Two-thirds fill a large beaker with water. This is needed for step 10.
Continue to gently warm the reaction mixture. Hold one of the dry boiling tubes in
position as shown in the diagram below. Notice that the ammonia is collected with the
boiling tube upside down. This is because ammonia is less dense than air.
Ammoina gas
Ammonium chloride
and calcium hydroxide
Delivery tube
Boiling tube
Figure 3.4: The equipment setup required to collect the ammonia gas.
Test around the open end of the collecting boiling tube with universal Indicator paper
to check that the collecting tube is full of ammonia.
Hold the tube of ammonia upside down then quickly put it, mouth still downwards,
into water in a beaker. The ammonia dissolves in the water and the level of the water
should rise up inside the test tube. If you want to try this a second time, use a fresh
dry boiling tube.
Ammoina gas
Water
Figure 3.5: Setup that shows ammonia gas dissolved in water

Observation and Analysis
A. Why the experiment could be carried out in a well-ventilated laboratory?
B. What is the purpose of putting the lump of calcium oxide into the boiling
tube containing the ammonium chloride/calcium hydroxide mixture?
C. How do you test with universal indicator paper to check that the collect-
ing tube is full of ammonia gas around the open end of the collecting
boiling tube?
D. What is the nature of ammonia is it alkaline or acidic gas, if it is alkaline
please write the reaction equation that shows its alkalinity?
130
Experiment 3.2
Ammonia Fountain Demonstration
Objective: To make a miniature chemical fountain using only soluble ammonia and
atmospheric pressure
Materials
Water, 2-L round bottomed flask, 2-L beaker, 2-hole stopper Medicine dropper or
10cm syringe, Glass tube (~2 ft. in length), Ring stand and clamps
Chemicals
NH4Cl and NaOH or NH4OH or dry NH3 gas, water and Phenolphthalein
Procedure:
1. Fill the 2-L flask with dry NH3 and seal with a rubber stopper. Be sure there is
no residual water on the walls of the flask prior to filling with gas. This can be
done by rinsing the walls with acetone and drying. NH3 can be obtained from
a tank or generated chemically. NH3 can be generated by gently heating (in a
hood) a 1:1 mixture of NH4Cl: NaOH in a glass tube. Another method involves
gently heating (in a hood) a small amount of concentrated NH4OH inside the
flask to be used.
2. Once the NH3 flask is filled, setup the demonstration as depicted in the figure
below. The glass tube should be about ½ inch from the bottom of the inverted
flask and cannot rest flat against the bottom of the flask. Fill the beaker with 1.5
L of water. To this, add 1 mL of indicator solution.
3. Remove the bulb from the medicine dropper and fill it with water. Place it back
on the dropper and squeeze the water into the flask. The NH3 gas will dissolve
in the water and cause the water from the beaker to rise into the flask. At this
point the phenolphthalein present will indicate a basic solution (pink).
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CHEMISTRY GRADE 12
Figure 3.6: Set-up of ammonia fountain demonstration Experiment

A. What will be the color of the phenolphthalein present in this solution? And the
color indicates what type of solution is it?
B. As ammonia (NH3) getting dissolved in the water what will happen?
Exercise 3.3
1. Write a balanced chemical equation for the formation of ammonia by
Haber process.
2. What is the purpose of adding finely divided iron in the Haber process?
3. Why high temperature conditions are required in production of ammonia
in Haber process?
4. Predict the product formed and write the reaction equation when you
heating an ammonium salt, such as ammonium chloride NH4Cl with a
strong alkali, such as sodium hydroxide or calcium hydroxide in laboratory.
132
3.3.2 Nitric Acid Manufacturing Process
Activity 3.4
Discuss in group and present your answer to the class.
1. Why nitric acid is considered as a highly corrosive mineral acid?
2. Why nitric acid is used for the manufacture of explosives such as
trinitrotoluene (TNT) and nitroglycerine?
Properties
Pure nitric acid has a density of 1.51 g/cm3. It is a colorless liquid, with an extremely pun-
gent odor, in appearance similar to water, but on exposure to light it turns brown because
of slight decomposition into NO2 (brown) and O2.
4 HNO3 ( l ) → 4 NO2 ( g ) + O2 ( g ) + 2 H 2O ( l ) brown
Nitric acid is a strong acid and dissociates completely to give H3O+ and NO3– in dilute aque-
ous solution. Nitric acid forms a large number of salts, called nitrates, which are typically
very soluble in water. Nitric Acid is a highly corrosive mineral acid. Nitric acid and its salts
are strong oxidizing agent, particularly when it is hot and concentrated. This fact explains
the violence of the reactions with metals, which result in the release of hydrogen. It reacts
readily with numerous substances and produces heat when dissolved in water. A significant
proportion of reactions involving it are even explosive.
Concentrated nitric acid is highly hazardous to health. Upon contact with the skin, it causes
severe burns and even necrosis.
Uses
Neutralization of nitric acid with ammonia results in ammonium nitrate – the most import-
ant component of mineral fertilizers used worldwide. In addition, HNO3 can be used for
soil acidification in horticulture. In the chemical industry, nitric acid is primarily a precur-
sor to organic nitrogen compounds, such as nitrobenzenes. When combined with aromatic
compounds, it yields substances used to make explosives such as TNT and nitroglycerine.
Another important application is rocket fuel. For this purpose, a mixture of HNO3, dini-
trogen tetroxide and hydrogen peroxide, also known as red fuming nitric acid, is prepared.
Nitric acid’s potential for plastic production is also noteworthy. Other, less popular uses of
nitric acid include:
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CHEMISTRY GRADE 12
• production of organic dyes and lacquers;
• pharmaceutical industry;
• production of fungicides;
• cleaning and etching of metal surfaces;
• refining of precious metals for the jewellery industry (in preparation of aquaria);
• the artificial ageing of wood to obtain the desired shade;
• production of household cleaning products;
• detection of traces of metals in laboratory test substances.
Preparation
Nitric acid can be obtained by reacting nitrogen dioxide with water. Under laboratory con-
ditions, an alternative production method is the reaction of potassium nitrate with sulphuric
acid to produce pure nitric acid.
2 KNO3 + H 2 SO4 → K 2 SO4 + 2 HNO3
(Salt of more volatile acid + less volatile acid → displaces more volatile acid). There is a
basic principle that a more volatile acid can be displaced from its salt by a less volatile acid.
For commercial purposes, the basic production method is the so-called Ostwald process.
This is the catalytic oxidation of ammonia to nitric oxide, which, using special absorption
towers, yields concentrated HNO3 acid. For purchase, a concentration of 65–68% is most
desirable.
Ostwald processes: The principle or mechanism behind the Ostwald process is “the con-
version of ammonia to nitric acid simply occurs as a result of oxidation. This particular
oxidation reaction gives us the corresponding nitric oxide. Further, when the nitric oxide is
oxidized nitrous gases are formed and those gases can trap water molecule. As a result, we
obtain nitric acid. Catalytic oxidation involving O2 is used where ammonia will give rise
to the product.”
Production of Nitric Acid

Nitric acid is produced industrially from ammonia by the three-step Ostwald process:
Step 1: Ammonia is burned in excess oxygen over a platinum catalyst to form nitricoxide
(NO):
4 NH 3 ( g ) + 5O2 ( g ) →
850 0c
5 atm , Pt
4 NO ( g ) + 6 H 2O( g )
134
Step 2: Additional air is added to cool the mixture and oxidize NO to NO2:
2 NO ( g ) + O2 ( g ) → 2 NO2 ( g )
Step 3: The NO2 gas is bubbled into warm water where it reacts to give nitric acid and nitric
oxide:
3 NO2 ( g ) + H 2O ( l ) → 2 NHO3 ( aq ) + NO ( g )
The nitric oxide (NO) is recycled in Step 2.
The production of nitric acid with the Ostwald process is summarized in Figure 3.7.
Figure 3.7: Simplified diagrams that shows Nitric acid manufacturing process
135
CHEMISTRY GRADE 12
Experiment 3.3
Preparation of Nitric Acid in Laboratory
Objective: This experiment gives an opportunity to prepare nitric acid
Equipment & Apparatus
Round-bottomed borosilicate flask (Preferably thick-walled), delivery tube, glass
stopper, glass retort, Tripod stand, Bunsen burner, ice cold water
Chemicals
Potassium Nitrate and concentrated sulphuric acid
Safety Precautions
Concentrated nitric acid is corrosive and oxidizing - wear goggles or face shield.
The use of nitrile gloves is recommended.
Procedure
1. 50gm of potassium nitrate (KNO3 ) + 25ml of concentrated sulphuric acid
(H2SO4) are taken in a round bottom flask.
2. The reactants are heated to about 200 taking care that the temperature does not
cross 200
3. The vapors of nitric acid are cooled and condensed to a brown liquid in a receiv-
er cooled under cold water. See its collection as shown in the diagram below.
Figure 3.8: Set-up of laboratory preparation of Nitric acid

A. What do you observe in the formation of nitric acid in this experiment?
B. Write a reaction equation that explains the formation of Nitric acid in this
experiment.
136
Experiment 3.4
Properties of Nitric Acid
Objective: This experiment gives an opportunity to see the acidic property of nitric
acid by taking place a dramatic reaction between copper and nitric acid.
Equipment & Apparatus
1 dm3 round-bottomed borosilicate flask (Preferably thick-walled), clamp stand, de-
livery tube 1 dm3 conical flask glass wool bowl or trough safety screens (if in open
lab).
Chemicals
5 g copper turnings and 40 cm3 concentrated nitric
Safety Precautions
Concentrated nitric acid is corrosive and oxidizing - wear goggles or face shield.
The use of nitrile gloves is recommended.
Procedure
1. Fill the conical flask with water and add the acid to the round-bottomed flask
2. Clamp the round bottomed flask into position and check that the delivery tube,
when in place, is at the bottom of the flask
3. Loosely plug the neck of the conical flask with glass wool, leaving the delivery
tube in position, ready to be removed when the copper is added
4. Add a trough or bowl under the round bottomed flask to catch any acid that may
leak if the glass fails.
5. Add the copper and fit the delivery tube. Lower the sash (if in a fume cupboard
6. After about 80 seconds the reaction will slow and the gases in the round-bot-
tomed flask with cool.
7. Add water drop by drop into the vessel and observe what is happened?
A. As the copper added, what color observed/developed in the solution?
B. What gas is evolved and what is the color of this gas.
C. Write the reaction equation which shown the reaction of copper with concentrat-
ed nitric acid?
D. The initial green color is associated with the copper when ligated by nitrate ions
in high concentration in the acid. *How the characteristic blue color in the foun-
tain developed
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CHEMISTRY GRADE 12
Exercise 3.4
1. Describe the properties of nitric acid.
2. Show the preparation of nitric acid by the Ostwald process.
3. What are the main uses of nitric acid?
4. Predict the product and write the reaction equation when you react
potassium nitrate with sulphuric acid .
3.3.3 Manufacturing of Sulphuric Acid
Activity 3.5
Which chemical do you think is produced in the largest volume in the world?
And why?
Properties
Anhydrous, 100% sulfuric acid is a colorless, odorless, heavy, oily liquid. It is heavier than
water with molar mass 98 gram/mole. Pure H2SO4 melts at 10.5 °C and boils at 338 °C,
where it decomposes by losing SO3 to give 98.3% H2SO4. It is soluble in all ratios with wa-
ter. This chemical is highly corrosive, reactive and is soluble in water. The sulphuric acid
can be diluted by water to get acids in various strengths for different purposes. During the
mixing process, sulphuric acid should be added to water not the other way around. Since
the dissolution of sulfuric acid in water is very exothermic i.e. a large amount of heat is
released and the solution may even boil. It has a very high oxidizing power and thus, acts as
a strong oxidizing and dehydrating agent. It can oxidize both metals as well as non-metals.
Moreover, it itself reduces to sulphur dioxide.
Example
Cu + 2 H 2 SO4 → CuSO4 + SO2 + H 2O

2 H 2 SO4 + C → 2 SO2 + CO2 + 2 H 2O
Common names and concentrations of H2SO4 are battery acid, 33.5% H2SO4 and chamber
or fertilizer acid, 62.18 %.
• Care must be taken during dilution of sulphuric acid
Uses
Sulfuric acid (H2SO4) is the largest volume chemical produced in the world. It is normally
manufactured at about twice the amount of any other chemical and is a leading economic
138
indicator of the strength of many industrialized nations. The rate of consumption of sul-
phuric acid is a measure of a country’s industrialization. Because of these facts sulphuric
acid has many uses:
• In fertilizer industry: It is used in the preparation of fertilizers such as ammonium
phosphate, ammonium sulphate, super phosphate of lime, etc.
• In petroleum refining: It is used for the refining of crude petroleum. The crude
• In chemical industry: It is used for the manufacture of hundreds of other compounds
such as hydrochloric acid, nitric acid, phosphoric acid, sulphates, bisulphates, diethyl
ether, etc.
• In metallurgy: Sulphuric acid is used for metallurgical processes such as electrolytic
refining, electroplating, galvanizing, etc. A number of metals like copper, silver, etc.
are extracted from their ores using sulphuric acid.
• It is used for cleaning the surfaces of metals (picking) before electroplating.
• It is used in the manufacture of explosive such as dynamite, T.N.T. nitro cellulose
products (gum, cotton), etc.
• It is also used as a drying and dehydrating agent. It is often used to dry neutral and
acidic gases such as nitrogen, oxygen, and carbon dioxide
• It is used for storage batteries as electrolyte

Preparation
Sulphuric acid is manufactured industrially by the contact Process which involves the fol-
lowing four major steps:
Step 1: Burning sulphur in air (preparation of sulphur dioxide):
S ( s ) + O2 ( g ) → SO2 ( g )
Step 2: Converting SO2 to SO3 (Oxidation of sulphur dioxide to prepare sulphur tri oxide)
2 SO2 ( g ) + O2 ( g ) 
  2 SO3 ( g )

V2O5
400℃
The conversion of SO2 to SO3 is slow, but it is increased by heating the reaction mixture to
400 in the presence of V2O5 catalyst. Because the SO2 and O2 molecules react on contact
with the surface of V2O5, the process is called Contact process.
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CHEMISTRY GRADE 12
Step 3: Passing SO3 into concentrated H2SO4 (addition reaction of sulphur trioxide and sulphuric
acid to give oleum):
SO3 ( g ) + H 2 SO4 ( l ) → H 2 S 2O7 ( l )
Sulphur trioxide is absorbed in to 98 % sulphuric acid to form oleum which is also known
as fuming sulphuric acid.
Step 4: Addition of water to oleum i.e. Dilution of oleum to produce concentrated sulphuric acid
H 2 S 2O7 ( l ) + H 2 O ( l ) → 2 H 2 SO4 ( l )
Oleum is diluted with water to form concentrated sulphuric acid as indicated in above re-
action.
The production of sulfuric acid with the contact process is summarized in Figure 3.9.
SO2 + O2 Concentrated
Sulpheric Acid
Sulpher
SO3
Furnace
SO2
H2S2O7 (Oleum) Pipe
Catalyst Converter
Contacting V2O5 catalyst Water
Air Dry H2SO4
at 450-550 o C
First Step Second Step Third Step
Figure 3.9: Production of sulfuric acid (contact process)
Exercise 3.5
1. Describe the industrial production of H 2SO 4. Write the equations and state
the conditions of each step.
2. State the properties and major uses of sulphuric acid.
3. Draw a schematic diagram that involves the four major steps in the
production of sulphuric acid along with chemical reaction.
4. When active metal reacts with concentrated sulfuric acid the active metal
gets oxidized while the sulphuric acid get reduced to H2S, S and SO2.
Predict the product formed and write the reaction equation “when eight
moles of aluminum react with 15 mole of conc. sulphuric acid”
140
3.3.4 Nitrogen Based Fertilizers
Activity 3.6
Discuss in group and present your opinion to your classmates.
1. Describe why a large-scale use of synthetic fertilizers can be harmful to
the environment
2. What is the purpose of adding nitrogen stabilizers in soil after addition of
nitrogen-based fertilizers?
3. What is the role of nitrifying bacteria related to the reaction of nitrogen-
based fertilizers?
The common forms of N based fertilizer include anhydrous ammonia, urea, urea-ammo-
nium nitrate (UAN) solutions and Diammonium Monohydrogen Phosphate (DAP) with
represented by a chemical formula (NH4)2HPO4.
Anhydrous Ammonia
Anhydrous ammonia (NH3) is the most basic form of N fertilizer. Ammonia, a gas at atmo-
spheric pressure, must be compressed into a liquid for transport, storage and application.
Consequently, it is applied from a pressurized tank and must be injected into the soil to
prevent its escape into the air.
Although almost 80 percent of the earth’s atmosphere is comprised of nitrogen, it is in

a chemically and biologically unusable form for plants. Using a complex method called
the Haber-Bosch process (refer section 3.3.1 for this process), nitrogen is captured from
the air, combined with a hydrogen source and converted into a form that can be used
by growing plants. Ammonia in this form is also known as ammonia gas or anhydrous
(“without water”) ammonia.
Application
Anhydrous ammonia is applied by injection 6 to 8 inches below the soil surface to mini-
mize escape of gaseous NH3 into the air. NH3 is a very hygroscopic compound and once in
the soil, reacts quickly with water and changes to the ammonium (NH4+) form. As a posi-
tively charged ion, it reacts and binds with negatively charged soil constituents including
clay and organic matter. Thus, it is held on the soil exchange complex and is not subject to
movement with water.
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CHEMISTRY GRADE 12
Soil reactions - Over time and with appropriate soil temperatures that support biological
activity, NH4+ ions are converted to the nitrate (NO3-) form by the action of specific soil bac-
teria in a process known as nitrification. Nitrification generally occurs at soil temperatures
above 50 , and increases as temperatures rise above this level. However, some limited ac-
tivity occurs below 50 as well. Ammonium is converted first to nitrite (NO2-) by the action
of Nitrosomonas bacteria, and then to nitrate by Nitrobacter and Nitrosolobus bacteria:
NH 4+ →
Nitosomonas
NO2−
Nitrobacteria
−
2 → NO3−
NO  &
Nitrosolobus
Urea
Urea is a solid fertilizer with high N content (46%) that can be easily applied to many types
of crops and turf. Its ease of handling, storage and transport, convenience of application by
many types of equipment, and ability to blend with other solid fertilizers has made it the
most widely used source of N fertilizer in the world.
Production
Urea is manufactured by reacting CO2 with NH3 in the following two step reactions:
2 NH 3 + CO2 → NH 2COONH 4 ( ammonium carbamate )
NH 2COONH 4 + ( NH 2 )2 + CO + H 2O ( urea + water )
The urea molecule has 2 amide (NH2) groups joined by a carbonyl (C=O) functional group.
Urea readily dissolves in water, including soil moisture. Thus, it can be “incorporated” into
the soil by sufficient rainfall or irrigation.
Soil Reactions - If urea is applied to the soil surface and not incorporated by water or till-
age, it is subject to volatilization losses of N. This occurs as urea undergoes hydrolysis to
carbon dioxide and ammonia:
142
( NH 2 ) 2 CO + H 2O → CO2 + 2 NH 3
Urea-ammonium nitrate (UAN) Solutions

Urea-ammonium nitrate (UAN) solutions are also popular N fertilizers. These solutions are
made by dissolving urea and ammonium nitrate (NH4NO3) in water.
Urea-ammonium nitrate (UAN) solutions are mixtures of urea, ammonium nitrate, and wa-
ter in various proportions. All common UAN solutions (28%, 30% and 32%) are formulat-
ed to contain 50% of actual N as amide, (from urea), 25% as ammonium (from ammonium
nitrate), and 25% as nitrate (from ammonium nitrate).
Production
Liquid urea-ammonium nitrate (UAN) fertilizer is relatively simple to produce. A heated

solution containing dissolved urea is mixed with a heated solution of ammonium nitrate to
make a clear liquid fertilizer. Half of the total N comes from the urea solution and half from
the ammonium nitrate solution.
Soil Reactions - The urea portion of UAN solutions reacts just as dry urea does (see the
reaction of urea). If applied on the surface, the amide-N in the solution may incur losses
due to volatilization when urease hydrolysis releases NH3. But if UAN is incorporated
by tillage or sufficient water, the NH3, quickly reacts with soil water to form NH4+. This
ammonium, as well as the ammonium N derived from ammonium nitrate in the solution,
adheres to soil components at the application site and is not subject to loss in the short term.
Like N applied as anhydrous ammonia, this N will eventually be taken up by plants in the
ammonium form, or if not, eventually converted to nitrate by soil bacteria.
Diammonium Monohydrogen Phosphate (DAP), (NH4)2HPO4
Diammonium monohydrogen phosphate (DAP) is a white crystalline compound.
Production
Diammonium monohydrogen phosphate (DAP) is formed by the reaction between ammo-
nia and phosphoric acid by the following two steps:
Step 1: Anhydrous ammonia reacts with phosphoric acid to form monoammonium dihy-
drogen phosphate and diammonium monohydrogen phosphate
3 NH 3 ( g ) + 2 H 3 PO4 ( l ) → NH 4 H 2 PO4 ( s ) + ( NH 4 ) 2 HPO4 ( s )
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CHEMISTRY GRADE 12
Step 2: Recycling monoammoniumdihydrogen phosphate for further reaction with anhy-

drous ammonia yields DAP:
NH 4 H 2 PO4 ( s ) + NH 3 ( g ) → ( NH 4 ) 2 HPO4 ( s )
DAP is used as a fertilizer. It temporarily increases soil acidity, but over the long term, the
soil becomes more acidic than before upon nitrification of the ammonium. DAP has the
advantage of having both nitrogen and phosphorus, which are essential for plant growth.
DAP can be used as fire retardant. It lowers the combustion temperature of the material,
decreases weight-loss rates, and causes an increase in the production of residue or char.
DAP is also used as a yeast nutrient in wine making and beer brewing.
Exercise 3.6
1. Write the chemical reaction that shows the synthesis of urea?
2. Write the reaction which shows soil reactions of urea?
3. Describe the industrial production of DAP. Write the chemical equations
too.
4. Describe the properties and major uses of DAP.
5. Calculate the percentage composition of phosphorus and nitrogen in DAP.
Project 3.1
What is the name of natural fertilizers that most of Ethiopian farmers use to increase the
soil fertility? And do you know how it is composed? Please collect information and submit
a report to your teacher.
3.3.5 Some Common Pesticide and Herbicides
Activity 3.7
Discuss in group and report your finding to your classmates. What are
the common pesticides and herbicides most frequently used by Ethiopian
framers?
Pesticides
Pesticides are chemicals used to prevent or control pests, diseases, weeds and other plant
pathogens. It decreases yield losses, and maintain high product quality. Chemical pesticides
can be classified according to their chemical composition. This method allows the uniform
144
and scientific grouping of pesticides to establish a correlation between structure, activity,

toxicity and degradation mechanisms, among other characteristics. Table 3.1, shows the
most important pesticides and their general characteristics, and Figure 3.10 show examples
of some chemical structures of pesticides.
Table 3.1: General characteristic of some pesticides
Pesticides Characteristics Main composition

Organochlo- Carbon atoms, chlo-
• Soluble in lipids
rines rine. hydrogen and ox-
• They accumulate in fatty tissue of ygen. They are nonpo-
animals. are transferred through the food lar and lipophilic
chain
• toxic to a variety of animals
• long-term persistence
Organophos- Possess central phos-
• Soluble in organic solvents but also in
phates phorus atom in the mol-
water ecule. In relation whit
• They infiltrate reaching groundwater, less organ chlorines, these
compounds are more
persistent than chlorinated hydrocarbons
stable and less toxic in
• some affect the central nervous system the environment. The
• They are absorbed by plants and then organophosphate pesti-
cides can be aliphatic,
transferred to leaves and stems which
cyclic and heterocyclic.
are the supply of leaf-eating insects or
feed on wise.
Carbamates Chemical structure
• Carbamate acid derivatives
based on a plant alka-
• kill a limited spectrum of insects loid Physostigma vene-
• highly toxic to vertebrates nosum
• Relatively low persistence

Pyrethroids Compounds similar to
• Affect the nervous system but less than
the synthetic pyrethrins
compared to the other pesticides (alkaloids obtained
• the safest in terms of their use from petals of Chysan-
themun cinerariefolium
• some are used as household insecticides
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CHEMISTRY GRADE 12
Biological Viruses, microorgan-

• Only the Bacillus thuringiensis (Bt)
isms or their metabolic
and its subspecies are used with some product
frequency
• are applied against forest pests and crops
• Particularly against butterflies and also
affect other caterpillars
Figure 3.10: Examples of chemicals structure of pesticides (A) Organochloride

(B) Pyrethroid (C) Carbamate (D) Organophosphate
On the other hand, there are also traditionally produced pesticides by Ethiopian farmers.
Traditionally, farmers of different districts produce pesticides from botanical origins and
then apply it to fruits, vegetables and other crops. These pesticides are called botanical
pesticides. Botanical pesticides are extracted from various plant parts (stems, seeds, roots,
leaves and flower heads) of different plant species. Botanical pesticides are hailed for hav-
ing a broad spectrum of activity, being easy to process and use, having a short residual
activity and for not accumulating in the environment or in fatty tissues of warm-blooded
animals. The following are some of the common natural pesticides commonly used in some
areas of Ethiopia: Neem Leaf, Salt Spray and Onion and Garlic Spray. Let us see the detail
146
of Neem Leaf which is one of traditionally produced pesticides.
Neem Leaf
Neem has long been used for its medicinal and culinary properties. It is also known to be
used as a deterrent to pests. This medicinal herb has a bitter taste and strong odour that may
keep the bugs away from your plants, but non-toxic to animals, birds, plants and humans.
It›s best to spray Neem oil on young plants where it is said to be effective for about 22 days.
Add some Neem oil to a dash of liquid soap and some warm water and stir slowly. Add it
to a spray bottle and use it immediately. This serves as an insect/pest repellant. Even you
can cut down and collect the Neem leaf around your environment and put it simply in your
home /table as it serves also as pests/insect repellant. Figure 3.11 shows a Neem leaf that
is grown in most gardens.
Figure 3.11: Neem Leaf (Azadirachta indica)
Project 3.2
Please collect information from your parents or concerned body and write a report about
one of the common traditionally produced pesticides by Ethiopian farmers other than Neem
Leaf. And submit the report to your teacher.
Herbicides (chemical weed killers)

Herbicides also commonly known as weed killers which are substances used to control
unwanted plants. Selective herbicides control specific weed species, while leaving the
147
CHEMISTRY GRADE 12
desired crop relatively unharmed. Non-selective herbicides (sometimes called total weed
killers in commercial products) since they kill all plant material with which they come into
contact. Herbicides have largely replaced mechanical methods of weed control in countries
where intensive and highly mechanized agriculture is practiced.
Types of Herbicides
The most important chemical groups of herbicides are chlorophenoxy acids such as 2,4-
D and 2,4,5-T; triazines such as atrazine, hexazinone, and simazine; organic phospho-
rus chemicals such as glyphosate; amides such as alachlor and metolachlor; thiocarbamates
such as butylate; dinitroanilines such as trifuralin; chloroaliphatics such as dalapon and tri-
chloroacetate; and inorganic chemicals such as various arsenicals, cyanates, and chlorates.
Exercise 3.7
1. What are insecticides?
2. List and describe the types of pesticides.
3. List the most common groups of herbicides?
3.3.6 3.3.7 Manufacturing of Sodium Carbonate
Activity 3.8
Discuss in groups for the following questions and present your opinion to the
class?
1. Do you know the raw material of glass production? How is it prepared?
2. Why do Solvay plant situated near water mass?
Properties
Sodium carbonate (washing soda) is a white crystalline solid powder. It exists as a decahy-
drate (Na2CO3. 10H2O) compound. It has a density of 2.54 g/cm3, a purity of > 98 %. It has
a high melting point 851°C and a high boiling point 1,600 °C. It has hygroscopic properties
in nature. There are two forms of sodium carbonate available, light soda and dense soda. It
can be easily dissolved in water to form an aqueous solution with moderate alkalinity and
dissolved in acids by liberating CO2. But it is insoluble in alcohol. Anhydrous Sodium Car-
bonate is unaffected by heat. It melts without disintegrating. The release of OH–(aq) ions
during hydrolysis makes Sodium Carbonate aqueous solutions somewhat alkaline.
Na2CO3 ( s ) + 2 H 2O ( l ) → H 2CO3 ( aq ) + 2 Na + ( aq ) + 2OH – ( aq )
148
Its aqueous solution has a property of absorbing carbon dioxide from the air, and produces
sodium Hydrogen Carbonate.
Na2CO3 ( aq ) + H 2O + CO2 ( g ) → 2 NaHCO3 ( aq )
Uses
Sodium carbonate has wide applications in various kinds of fields around the world. One
of most important application of sodium carbonate is for the manufacturing of glass. Based
on statistics information, about half of the total production of sodium carbonate is used for
the manufacturing of glass. During the production of glass, sodium carbonate acts as a flux
in the melting of silica. It is also largely used in production of detergents and soaps. In ad-
dition, as a strong chemical base, it is used in the manufacturing of pulp and paper, textiles,
drinking water. In addition, it can also be used for tissue digestion, dissolving amphoteric
metals and compounds, food preparation as well as acting as a cleaning agent. It is also
used in the brick industry.
Production Method (Solvay process)

Sodium carbonate at present is mostly mined from its natural deposits. It also is manu-
factured synthetically by Solvay (or ammonia-soda) process. The natural production of
sodium carbonate currently has surpassed its synthetic production.
The Solvay process involves a series of partial reactions. The first step is calcination of
calcium carbonate to form lime and CO2. Lime is converted to calcium hydroxide. The
most crucial step of the process involves reacting brine solution with carbon dioxide and
ammonia to produce sodium bicarbonate and ammonium chloride. Sodium bicarbonate
converts to sodium carbonate. The calcium hydroxide and ammonium chloride react to
form calcium chloride as the by-product. The partial reactions are shown below:
CaCO3 → CaO + CO2
CaO + H 2O → Ca ( OH )2
2 NaCl + 2CO2 + 2 NH 3 + 2 H 2O → 2 NaHCO3 + 2 NH 4Cl
2 NaHCO3 → Na 2CO 3 + H 2O + CO2
Ca ( OH )2 + 2 NH 4Cl → CaCl2 + 2 NH 3 + 2 H 2O
The overall reaction:
CaCO3 + 2 NaCl → Na 2CO 3 + CaCl2
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CHEMISTRY GRADE 12
Exercise 3.8
List the four major raw materials that are used to manufacture Na 2CO 3 in the
Solvay process.
1. What is the main byproduct in manufacturing of Na2CO 3 in the Solvay
Process?
2. Write the chemical equation of the reaction when sodium hydrogen
carbonate is heated in the Solvay process.
3. What is the purpose of burning coke in the Solvay process?
4. Write the chemical formula of the following compounds:
A) Washing soda b) soda ash c) baking soda
3.3.7 3.3.8 Manufacturing of Sodium Hydroxide NaOH
Activity 3.9
Discuss in groups and present your opinion to the class.
1. During the manufacturing process of NaOH from brine, Cl 2 is produced in
the process. What are the uses of this Cl 2?
2. Why we have to take care while doing experiments that involves sodium
hydroxide?
Properties
Sodium hydroxide (NaOH) is a white, translucent crystalline solid with a melting point of
591 k. It is a stable compound. NaOH is often referred to as caustic soda, due to its cor-
rosive action on many substances: it decomposes proteins at room temperatures and may
cause chemical burns to human bodies. It dissolves readily in water and moderately soluble
in alcohol; its solution has bitter and has a soapy feeling”. It is strongly alkaline in nature
commonly used as a Base.
Uses
It is widely used in numerous industrial processes such as in pulp and paper manufacturing,
alumina extraction from bauxite in aluminum production, as well as in the textiles industry
and drinking water production. NaOH is also an important compound in the manufacture
of soaps and detergents (i.e. a cleansing agent and in the manufacturing of washing soda),
in waste gases scrubbing, saponification and etherification and esterification reactions; as
150
well as in basic catalysis.
Preparation (Manufacturing process)

NaOH does not occur in nature. It has been manufactured at large scale for many years
from readily obtainable raw materials. It is manufactured from sodium chloride (NaCl) and
water (H2O) in electrolysis process. Its preparation involves various methods like;
1. Castner-Kellner process
2. Nelson Diaphragm cell
3. Loewig’s process
Castner-Kellner process
Principle: In the Castner-Kellner method, electrolysis of brine solution is performed in order to
obtain sodium hydroxide.
Castner-Kellner cell: It is a steel tank that is rectangular. Ebonite is lined inside the tank.
Titanium acts as an anode and a layer of mercury at the bottom of the tank acts as the cathode.
Ionization of brine solution occurs according to the following reaction:
2 NaCl → 2 Na + + 2Cl −
When the brine solution comes in contact with electric current, ionization takes place. As a
result positive and the negative ions move towards the electrodes. Sodium ions get depos-
ited at the mercury cathode forming a sodium amalgam. Chlorine ions move towards the
anode and exit the cell from the top.
Reaction at the anode: 2Cl − 2Cl − → Cl2 + 2e −
Reaction at the cathode: 2 Na + + 2e − → 2 Na
Formation of NaOH
The amalgam formed is then transferred to another chamber called denuder. In the denuder,
it is treated with water to obtain a sodium hydroxide solution. On evaporation of the solu-
tion, solid sodium hydroxide is formed. This is a very efficient process in order to obtain
pure caustic soda.
Do you know where caustic soda (NaOH) is manufactured in Ethiopia?
Mercury is toxic so care must be taken to prevent mercury losses.
Safety
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CHEMISTRY GRADE 12
 Due to its strong corrosive qualities, exposure to sodium hydroxide in its solid or
solution form can cause skin and eye irritation
 Pure NaOH has a high affinity for water and may form hydrates depending on the
concentration. Since some hydrates have melting points greater than 0 °C, insula-
tion or heating during storage.
Exercise 3.9
1. List the uses of NaOH in industrial process or manufacturing of other
valuable products
2. What is the role of caustic soda in the industrial cleaning process?
3. What are the health effects of caustic soda?
3.4 Some Manufacturing Industries in Ethiopia

 list some manufacturing industries in Ethiopia
 outline the important steps in the productions of ceramics
 mention some uses of ceramics
 outline the important steps in the production of cement, ceramics and
glass
 outline the important steps in the production of sugar and alcoholic
beverages
 predict the product produced when sugar undergoes
fermentation
 prepare local alcoholic beverages from the available
ingredients
 outline the important steps in the production of pulp and paper, soaps
and detergent and dry detergents
 explain how tanning is carried out;
 describe the application of the chemical preservation of skin and
hides;
 mention some uses of skin and hides;
 explain the process of food packing and preservation;
 present a report to the class after visiting a nearby food
factory
152
Some Manufacturing Industries in Ethiopia
Activity 3.10
1. Do you know where in Ethiopia most of chemicals /manufacturing
industries are located?
2. List as many of the manufacturing chemical industries in
3. Ethiopia, and write the products manufactured by them in tabular form?
The chemical industry in Ethiopia is still at a nascent stage. Therefore, there is a strong
demand to develop the chemical industry to meet the requirements of the rapidly growing
Ethiopian economy. Currently, imports fulfill domestic demand for chemicals/manufac-
turing products. According to CSA’s raw data for the year 2014, in Ethiopia, more than
153 chemical and chemical-related product manufacturing industries are available in the
country.
In this subsection emphasis is given to the production of final products like glass, cement,
ceramics, sugar, alcoholic beverages, food packing and preservation, soaps and dry deter-
gent, tanning and paper.
3.4.1 3.4.1 Glass Manufacturing
Activity 3.11
Discuss the following questions in groups and present your answer to the
class.
1. What is glass?
2. List the types of glasses with their corresponding main functions.
3. Is glass manufactured in Ethiopia?
Glass is an amorphous or non-crystalline solid material. It is inexpensive to make, easy to

shape when it’s molten, reasonably resistant to heat when it’s set, chemically inert (glass jar
doesn’t react with the things inside it). It can be recycled any number of times. The main
component of glass is silica.
Quartz glass is made by melting pure silica, SiO2, at a temperature of about 2300°C and
pouring the molten viscous liquid into moulds. It is of high strength, low thermal expansion
and highly transparent.
Soda-lime glass is ordinary glass. It is a mixture of sodium silicate and calcium silicate.
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CHEMISTRY GRADE 12
It is made by heating a mixture of silica sand, sodium carbonate or sodium sulphate and
limestone. The reactions that take place in forming soda-lime glass are the following:
Na2CO3 + SiO2 → Na2 SiO3 + CO2
CaCO3 + SiO2 → CaSiO3 + CO2
Soda-lime glass accounts for about 90% of manufactured glass. This type of glass is widely
used for window panes, bottles, dishes etc.
Borosilicate glass is commonly known as Pyrex. It is manufactured using boron (III) ox-
ide, B2O3, instead of limestone or calcium oxide. This glass has high resistance to chemical
corrosion and temperature changes and is widely used to make ovenware and laboratory
equipment such as flasks, beakers, and test tubes.
Projects 3.3
Have you ever wondered how glass retains different colors? Consult books in your library
and make list of the compounds added to impart color to the glass. Submit your findings to
your teacher?
Steps in glass production

i) Batch preparation: refers to the preparation of the raw materials according to the
appropriate combinations. The raw materials are mixed in a proportion of 60%
sand, 21% sodium carbonate and 19% limestone.
ii) Glass melting: The raw materials and recycled glass (according to their colour)
are fed into a glass-melting furnace. The materials are then heated to a tempera-
ture of about 1600°C to form a molten viscous liquid. Why glasses are separated
according to the colour?
The furnace operates continuously, producing glass 24 hours a day. Substances
that give the glass different colours or improved chemical and physical proper-
ties such as transparency, thermal and chemical stability and mechanical strength
are added during this process.
iii) Glass forming: This is the stage in which the melted glass is made into a required
shape.
iv) Annealing: This is a process that involves the removal of internal stresses by
reheating the glass followed by a controlled slow-cooling cycle during which
the stresses are relieved.
v) Inspection: It involves testing of the glass product to check whether it fulfills
desired quality requirements or not.
154
vi) Packing and dispatching is the final stage before distribution
Exercise 3.10
1. Predict the type of glass produced if potassium carbonate is used instead
of sodium carbonate? What would be its properties?
2. What type of color will impact by the iron compounds which is often
contained as impurities in the sand used in manufacturing of ordinary
glass?
3. To produce glass industrially two types of furnaces are used, what are the
two types of furnaces and what type of glass is produced in each type?
3.4.2 Manufacturing of Ceramics
Activity 3.12
Form a group of three to discuss the questions below and share your
reflection’s to the class
1. Discuss the traditional pottery industry in Ethiopia and present your
answer to the class?
2. List the similarities and differences between pottery and Ceramics.
3. Prepare a list of ceramics products used in daily life.
Ceramic is an inorganic, non-metallic solid prepared by the action of heat and subsequent
cooling. Traditional ceramics, such as porcelain, tiles and pottery are formed from min-
erals such as clay, talc and feldspar. Most industrial ceramics, however, are formed from
extremely pure powders of specialty chemicals, such as silicon carbide, alumina, barium
titanate, and titanium carbide.
The minerals used to make ceramics are dug out of the earth and are then crushed and
ground into a fine powder. Manufacturers often purify this powder by mixing it in a solu-
tion and allowing a chemical precipitate (a uniform solid that forms within a solution) to
form. The precipitate is then separated from the solution. The powder is heated to drive off
impurities including water.
The steps of manufacturing ceramics include:

A. Moulding: After purification, small amounts of wax are often added to bind the ceramic
155
CHEMISTRY GRADE 12
powder and make it more workable. Plastics may also be added to the powder to
give the desired pliability and softness. The powder can be shaped into different
objects by various moulding processes.
B. Densification: The process of densification uses intense heat to condense a ceramic ob-
ject
into a strong, dense product. After being moulded, the ceramic object is heated in an elec-
tric furnace to temperatures between 1000 °C and 1700 °C. As the ceramic heats, the pow-
der particles coalesce, much as water droplets join at room temperature. As the ceramic
particles merge, the object becomes increasingly dense, shrinking by up to 20 percent of
its original size. The goal of this heating process is to maximize the strength of ceramic by
obtaining an internal structure that is compact and extremely dense.
In general, most ceramics are hard and wear-resistant, brittle, refractory, thermal and elec-
trical insulators, non-magnetic, oxidation-resistant, and chemically stable. Due to the wide
range of properties of ceramic materials, are used for a multitude of applications.
• Well-known uses of ceramics: - they are commonly found in art sculptures, dishes,
platters and other kitchenware, kitchen tiles and bath room structures.
• Lesser-known uses for ceramics: - they are used as electrical insulators, computers
parts, tools, dental replacements, engine parts, and tiles on space shuttles and to
replace bones such as the bones in hips, knees and shoulders.
• Future uses of ceramics: - In future, the ceramics might be used to remove impurities
from the drinking water, and to replace diseased heart valves.
Do you know a ceramic industry in Ethiopia?
Figure 3.12 shows some photos of ceramics and pottery products in Ethiopia.
156
Figure 3.12: Some ceramics and pottery products in Ethiopia (A and C) Ceramic (b)
Pottery
3.4.3 Cement
Activity 3.13
Discuss in groups and present your answer to the class:
1. Is there any cement factory in Ethiopia? If there, where are they located?
2. Why Cement manufacturing plants are preferably located close to the
sources of the raw material?
3. Why most cement factories are located in rural areas of Ethiopia?
Cement production has been increasing because of the opening of new cement companies
and also the upgrade of the old ones.
Availability of cement raw materials in Ethiopia

The raw materials for the production of cement are limestone, clay, silica sand, gypsum,
calcium silicate, calcium aluminate, iron (III) oxide, magnesium oxide and pumice. Lime-
stone is the major ingredient for the production of cement. It is abundantly available in
Africa. Ethiopia has huge amounts of reserve raw materials.
Manufacturing Process
Cement is made by heating limestone (chalk), alumina (Al2O3) and silica-bearing materials
such as clay to 1450 °C in a kiln. This process is known as calcination. Calcination results
a hard substance called clinker. The clinker is then ground with a small amount of gypsum
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CHEMISTRY GRADE 12
into a powder. The resulting cement is known as Ordinary Portland cement (OPC).
When gypsum is included in the process, cement known as Portland cement is produced.
Portland cement was first discovered in England. On setting, it hardens to a stone-like mass
and was compared to the famous Portland Rock of England.
Figure 3.13: Cement manufacturing process.
Upper Part of the Kiln


Raw Material  → Complete elimination of moisture
Middle Part of the Kiln
Limestone decomposes to calcium oxide
CaCO3 ( s ) 

→ CaO ( s ) + CO ( g )
Lower End of the Kiln In this part,
The temperature reaches about 1600 °C; the partly fused and sintered mixture undergoes a
series of chemical reactions to form calcium aluminates and silicates.
2CaO + 2 SiO2 → 2CaO.SiO2 ( di − calcium silicate )
3CaO + 3SiO2 → 3CaO.SiO2 (tri − calcium silicate)
CaO + 3 Al2O3 → 3CaO. Al2O3 ( tri − calcium aluminate )
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4CaO + 4 Al2O3 + 4 Fe2O3 → 4CaO. Al2O3 . Fe2O3 ( tetra calcium aluminate ferrate )
MgO + SiO2 → MgSiO3 ( Magnesium silicate)
The resulting mixture of all these silicates and aluminates is called cement clinker. After
cooling, it is mixed with 2-3% gypsum (calcium sulphate) and ground to a fine powder.
Gypsum slows down the rate of setting of cement, so that the cement hardens adequately.
Table 3.2 The approximate composition of cement
Component Percentage %
Calcium oxide (CaO) 50-60
Silica (SiO2) 20-25
Alumina(Al2O3) 5-10
Magnesium Oxide (MgO) 2-3
Ferric oxide (Fe2O3) 1-2
Sulphur trioxide(SO3) 1-2
Setting of Cement
When cement mixed with water, the cement first forms a plastic mass that hardens after
sometime. This is due to the formation of three-dimensional cross-links between –Si–O–
Si– and –Si–O– Al– chains. The first setting occurs within 24 hours, whereas the subse-
quent hardening requires about two weeks. In the hardening process of cement, the transi-
tion from plastic to solid state is called setting.
Project 3.3
Take a 0.5 kg of cement and mix it with correct proportion of sand and water. Mix the com-
ponent well till a plastic mass is formed. Take this plastic mass and construct a model of
any object. Start pouring water on the model starting from the second day onwards. Report
the observations to the class 24 hours later and with the same procedure check any changes
happened after two weeks.
3.4.4 Sugar Manufacturing
Activity 3.14
Work in pairs and reflect your answers to the whole class
1. List the foods and drinks in which sugar is an ingredient.
2. List the different sources of sugar?
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CHEMISTRY GRADE 12
Sugarcane is a perennial herb belonging to the grass family. Native to tropical and subtrop-
ical regions of the world, this tropical grass is about 3 meters tall. And it is used commonly
as raw material for production of sugar.
Planting: Sugarcane is planted in fields by workers or mechanical planters. Typical cane

soil is made from the mixture of silts, clay particles and organic matter. Fertilizers are ap-
plied from the time of planting up until the beginning of the ripening period, depending on
the region where the crop is planted. Cane seasons last from 8-22 months.
1. Collecting the Harvest: Mature canes are gathered by a combination of manual and
mechanical methods. The cane is cut at ground level, the leaves are removed, the top is
trimmed off (by cutting off the last mature joint) the canes and transported to a sugar fac-
tory.
2. Cleansing and Grinding: The stalks are thoroughly washed and cut at the sugar mill.
After the cleaning process, a machine led by a series of rotating knives, shreds the cane
into pieces. This is known as “grinding”. During grinding, hot water is sprayed onto the
sugarcane to dissolve the remaining hard sugar. The shredded cane is then spread out on a
conveyer belt.
3. Juicing: The shredded sugarcane travels on the conveyor belt through a series of heavy-du-
ty rollers which extract juice from the pulp. The pulp that remains, or “bagasse”, is dried
and used as a fuel. The raw juice moves on through the mill to be clarified.
4. Clarifying: Carbon dioxide and milk of lime are added to the liquid sugar mixture, which
is heated until boiling. The process of clarifying begins at this stage. As the carbon dioxide
moves through the liquid, it forms calcium carbonate which attracts non-sugar debris (fats,
gums and waxes) from the juice, and pulls them away from the sugar juice. The juice is then
pushed through a series of filters to remove any remaining impurities.
5. Evaporation: The clear juice that results from the clarifying process is put under a vacu-
um where the juice boils at a low temperature and the water in it begins to evaporate. It is
heated until it forms into thick, brown syrup.
6. Crystallization: Crystallization is the process of evaporating the water from the sugar
syrup. Pulverized sugar is fed into a sterilized vacuum pan. As the liquid evaporates, crys-
tals form. The remaining mixture is a thick mass of large crystals. These crystals are sent
to a centrifuge that spins and dries them. The dried product is raw sugar, which is edible.
7. Refinery: Raw sugar is transported to a cane sugar refinery for the removal of molasses,
minerals and other non-sugars that contaminate it. This is known as the purification pro-
160
cess. Raw sugar is mixed with a solution of sugar and water to loosen the molasses from
the outside of the raw sugar crystals, producing a thick matter known as “magma”. Large
machines then spin the magma, separating the molasses from the crystals. The crystals are
promptly washed, dissolved and filtered to remove impurities. The golden syrup that is
produced is then sent through filters, and SO2 is passed through it to remove the colour and
water. The process of removing colour is known as bleaching. What is left is concentrated,
clear syrup which is again fed into a vacuum pan for evaporation.
8. Separation and packaging: Once the final evaporation and drying process is done, screens
separate the different- sized sugar crystals. Large and small crystals are packaged and la-
belled as white refined sugar.
Exercise 3.11
1. Write the chemical formula of the common sugar i.e. sucrose?
2. In Ethiopia most sugar industries produced byproducts in their sugar
production process? List the main byproducts?
3.4.5 Paper and Pulp
Activity 3.15
Discuss the following issues in groups of three and present it to your
classmates:
1. Wasting paper is like chopping down trees. Comment.
2. Some papers are cheap while others are expensive. What could be the
reason?
Do you know what this textbook is made of?
Paper is not a chemical compound which can be expressed by a chemical formula. Paper
is a mixture made from rags and wood pulp glued together with some additives, bleached
and dried.
Wood pulp is a dry fibrous material. The timber resources used to make wood pulp are re-
ferred to as pulp wood. Wood pulp is made from soft-wood trees, such as spruce, pine, fir,
larch and hemlock, and from hard woods, such as eucalyptus, aspen and birch.
Wood is composed of cellulose, lignin, oils and resins. Lignin is used to bind fibres of
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CHEMISTRY GRADE 12
cellulose together. To provide wood pulp, the cellulose must be separated from the lignin.
Manufacturing of pulp and paper involves the following steps
1. Harvesting: trees involves the cutting down of trees from their growing areas and trans-
porting the timber to the paper and pulp industry.
2. Preparation: for pulping is a step in which the bark of the tree is removed and then the
wood is chipped and screened to provide uniform sized chips (pieces).
3. Pulping is a step used to make wood pulp from the chipped wood pieces. This can be
accomplished by either mechanical or chemical means depending on the strength and
grade of paper to be manufactured.
A. Mechanical pulping: It utilizes steam, pressure and high temperatures instead of

chemicals to tear the fibres. The fibre quality is greatly reduced because mechanical
pulping creates short, weak fibres that still contain the lignin that bonds the fibres
together. Paper used for newspapers are a typical product of mechanical pulping.
B. Chemical pulping: Chemical pulp is produced by combining wood chips and
chemicals in large vessels called digesters. Heat and the chemicals break down the
lignin which binds the cellulose fibres together without seriously degrading the cel-
lulose fibres. Chemical pulp is manufactured using the Kraft process or the Sulphite
Process.
I) The Kraft Process is the dominant chemical pulping method. It is the most widely used
method for making pulp from all types of trees. The process uses aqueous sodium hydrox-
ide and sodium sulphide as a digestion solution. After digestion for about four hours at a
temperature of 170, the pulp is separated by filtration. This process uses a basic digestion
medium.
II) The Sulphite Process uses a cooking liquor (digestion) solution of sodium bisulphate or
magnesium bisulphate digester at pH of about 3 in a pulp. The action of the hydrogen sul-
phide ions at 60 over 6 to 12 hours dissolves the lignin and separates it from the cellulose.
After the process is complete, the pulp is recovered by filtration. The wood pulp achieved
from the Sulphite or Kraft processes is washed to remove chemicals and passed through a
series of screens to remove foreign materials
1. Bleaching: It is the process of removing colouring matter from wood pulp and increas-
ing its brightness. The most common bleaching agents are strong oxidizing agents such
as chlorine, chlorine oxide, ozone and hydrogen peroxide.
2. Making paper from pulp: After bleaching, the pulp is processed into liquid stock that
can be transferred to a paper mill. The suspension is poured onto a continuously moving
162
screen belt and the liquor is allowed to seep away by gravity to produce paper sheet. The
continuous sheet then moves through additional rollers that compress the fibres and
remove the residual water to produce fine paper.
3.4.6 Tannery
Activity 3.16
Discuss in groups and present your answer to the class.
1. The leather products of Ethiopia are durable and relatively cheaper than
the same products imported from outside. Why do people prefer to buy
imported products? What can you suggest to change this attitude? Discuss
this matter in class in relation to quality and availability of resources.
2. Why are leather products being replaced by synthetic products?
3. Do you know the traditional way of Tanning in Ethiopia? What are the
procedures to be followed when it is compared to the modern method?
Tanning is a process of converting raw animal hides and skin to leather, using tannin.
Leather is a durable and flexible material created by the tanning of animal hides and skin.
Tannin is an acidic chemical that permanently alters the protein structure of a skin so that it
can never return to raw hide or skin again.
Leather production involves various preparatory stages, tanning, and crusting
1. Preparatory stages are those in which the hide or skin is prepared for tanning. This stage
includes curing, soaking, flesh removal, hair removal, scudding, and deliming.
d) Curing: This process involves salting or drying the hide once it has been removed
from the animal. Curing is employed to prevent putrefaction of the protein sub-
stance, collagen, from bacterial infection. Curing also removes excess water from
the hide and skin. Brine curing is the simplest and fastest method.
e) Soaking: In this process, cured hides are soaked in water for several hours to sever-
al days to remove salt, dirt, debris, blood and excess animal fat from the skin.
f) Flesh removal: In this process, animal hides are moved through a machine that
strips the flesh from the surface of the hide.
g) Hair removal: In this step, the soaked hides and skins are transported to large vats
where they are immersed in a mixture of lime and water. This process is called
liming. It loosens the hair from the skin and makes hair-removal easier. After 1–10
days soaking, the hair is mechanically removed from the hide by a hair-removing
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CHEMISTRY GRADE 12
machine.
h) Scudding: This is the process in which hair and fat missed by the machines are
removed from the hide with a plastic tool or dull knife.
i) Deliming: This process involves the removal of lime from the skin or hides in a vat
of acid. After this preparatory process, the skin or hide is ready for tanning.
2. Tanning is a process that converts the protein of the raw hide or skin into a stable mate-
rial. There are two main types of tanning:
a) Vegetable or natural tanning: The skin is placed in a solution of tannin. Tannins

occur naturally in the barks and leaves of many plants. The primary barks used
in modern times are chestnut, oak, tanoak, hemlock, quebracho, mangrove, wattle
(acacia) and myrobalan. Naturally tanned hide is flexible and is used for making
shoes, luggage and furniture.
j) Mineral tanning: In this process, the skin is placed in solutions of chemicals such
as chromium sulphate and other salts of chromium. Chrome tanning is faster than
natural (vegetable) tanning and requires only twenty four hours. The leather is
greenish-blue in colour derived from the chromium. This process produces stretch-
able leather that is used for making garments and handbags.
3. Crusting: This is the final stage in leather manufacturing and includes dyeing, rolling
the leather to make it strong, stretching it in a heat-controlled room and performing a
process that involves covering the grain surface with chemical compounds such as wax,
oil, glazes etc. to make the leather very attractive.
3.4.7 Food Processing and Preservation
Activity 3. 17
What could be the reason for the rate of spoilage of food is faster in open air
in comparison to foods kept inside the refrigerator. Discuss in groups and
present your finding to the class.
Food preservation is the process of treating and handling food to stop or greatly reduce
spoilage, loss of quality, edibility or nutritive value caused or accelerated by microorgan-
isms. Preservation usually involves preventing the growth of bacteria, fungi and other mi-
croorganisms, as well as reducing the oxidation of fats which causes rancidity.
164
Activity 3.18
Discuss in groups and present it to the class.
1. What are the traditional methods used to preserve food for a long time
without spoil at your home?
2. What modern methods of food preserving and processing do we use in
Ethiopia.
Modern methods of food preservation are:
A. Freezing: This is one of the most commonly used processes, commercially and
domestically, for preserving a very wide range of foods such as potatoes, as well as
prepared foodstuffs that would not require freezing in their normal state.
B. Freeze-drying: Water vapour has easier access through the cell structure of any
product compared to water-penetrating the product and evaporating from the sur-
face of the product as in case of other drying methods. The gentle escape of water
vapour in the freeze-drying process leaves the product close to its original shape,
taste, and colour and there is no loss of aroma or flavour. For example, liquids such
as coffee, tea, juices and other extracts, vegetables, segments of fish and meat prod-
ucts. Freeze-drying is a superior preservation method for a variety of food products
and food ingredients.
C. Vacuum-packing: Stores food in a vacuum environment, usually in an air-tight
bag or bottle. The vacuum environment strips bacteria of the oxygen needed for
survival, slowing down the rate of spoiling. Vacuum-packing is commonly used for
storing nuts to reduce loss of flavour from oxidation.
Inorganic and organic preservatives
Activity 3.19
Discuss in groups about the traditional method of preserving meat and present
your answer to the class?
Some inorganic and organic preservatives are available for food preservation. Some exam-
ples of inorganic preservatives are sodium chloride (NaCl), nitrate and nitrite salts, sulfites,
and sulfur dioxide (SO2). NaCl lowers water activity and causes plasmolysis by withdraw-
ing water from cells. Nitrites and nitrates are curing agents for meats (hams, bacons, sausag-
es, etc.) to inhibit C. botulinum under vacuum packaging conditions. Sulfur dioxide (SO2),
sulfites (SO3), bisulfite (HSO3), and metabisulfites (S2O5) form sulfurous acid in aqueous
solutions, which is the antimicrobial agent. Sulfites are widely used in the wine industry
to sanitize equipment and reduce competing microorganisms. Wine yeasts are resistant to
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CHEMISTRY GRADE 12
sulfites. Sulfites are also used in dried fruits and some fruit juices. Sulfites have been used
to prevent enzymatic and nonenzymatic browning in some fruits and vegetables (cut pota-
toes).
A number of organic acids and their salts are used as preservatives. These include lactic
acid and lactates, propionic acid and propionates, citric acid, acetic acid, sorbic acid, and
sorbates, benzoic acid and benzoates, and methyl and propyl parabens (benzoic acid deriv-
atives).
For example, propionic acid and propionate salts (calcium most common) are active against
molds at pH values less than 6. They have limited activity against yeasts and bacteria. They
are widely used in baked products and cheeses. Acetic acid is found in vinegar at levels
up to 4–5%. It is used in mayonnaise, pickles, and ketchup, primarily as a flavoring agent.
Acetic acid is most active against bacteria, but has some yeast and mold activity, though
less active than sorbates or propionates.
3.4.8 Manufacturing of Alcoholic Beverages
Activity 3.20
Discuss the following questions in group and present your answer to your
classmates.
1. List the most common local alcohol beverages that are produced in most
of Ethiopian homes during a holiday?
2. What does fermentation in the absence of oxygen mean?
Ethanol is one of the constituents of all alcoholic beverages. ‘Tella’, ‘Tej’, beer, wine, ‘Ka-
tikalla’, ouzo, gin and whisky contain ethanol. There are a number of methods for preparing
ethanol using different materials. Since it is the constituent of all alcoholic beverages it is
better to describe its industrial preparation.
Industrial preparation of Ethanol

Ethanol is manufactured industrially by:
1. Fermentation of carbohydrates such as sugar: Fermentation is the slow decomposition

of carbohydrates such as sucrose, starch and cellulose in the presence of suitable en-
zyme that results in the formation of ethanol and carbon dioxide.
166
C12 H12O11 

Invertase
→ C6 H12O6 + C6 H12O6
Sucrose Glucose Fructose
C6 H12O6 + H 2O 
Yields
→ 2CH 3CH 2OH + 2CO2
Glu cos e Ethanol
Fermentation can produce an alcoholic beverage whose ethanol content is 12 – 15% only.
The alcohol kills the yeast and inhibits its activity when the percentage is higher. To pro-
duce beverages of higher ethanol content, distillation of the aqueous solution is required.
Most liquor factories in Ethiopia use molasses, a by-product of sugar industries, as a raw
material to produce ethanol. In the brewing industry, germinated barley called malt (in Am-
haric, ‘Bikil’) is used as the starting material. The whole process taking place in breweries
is summarized as follows:
Diastase nH O
2(C6H10O5)n + nH2O nC H O
12 22 11
2 2nC6H12O6
Maltase
Starch Maltose Glucose
C6H12O6 Zymase +
CH3CH2OH CO2
Glucose Ethanol
2. Catalytic Hydration of Ethene: Most ethanol is manufactured at present by this method.

In this process, ethene is treated with steam at 573 K and 60 atm pressures in the pres-
ence of phosphoric acid, H3PO4, catalyst.
(g) H3PO4
CH2 CH2 + H2O (g) CH3CH2OH (g)
573 k/60 atm Ethanol
Ethene
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CHEMISTRY GRADE 12
Experiment 3.5
Preparation of Ethanol by Fermentation
Objective: To prepare ethanol from sugar.
Materials required: Conical flask, glass rod, distillation flask, condenser, spatu-
la, thermometer, watch glass, and Bunsen burner, beaker, and stopper and delivery
tube.
Chemicals Required: Sugar, ammonium phosphate or ammonium sulphate, yeast,
Ca (OH)2.
Procedure:
1. Take 50 mL of distilled water in a conical flask, add 15 g of sugar to it and stir. Add
about 1 gram of yeast and a small amount of ammonium phosphate or ammonium
sulphate to the solution. Arrange the set-up, as shown below, and let the flask
stand for three days at a warm place.
Figure 3.14: The Fermentation of sugar

A. What is the purpose of adding yeast to the solution?
B. Why do we add ammonium phosphate or ammonium sulphate to the sugar
solution?
C. What happened to the calcium hydroxide solution at the end of the first or sec-
ond day? Which gas is produced?
D. What is the smell of the solution in the flask after three days?
E. What has happened in the flask containing the sugar solution as it stood for three
days?
2. After three days, filter the solution, and arrange the set up as in Figure 1.14.
Pour 20 mL of the filtrate in a distilling flask, heat the solution, and collect the
liquid in a receiver.
168
Figure 3.15: Separation of ethanol by distillation

Points to observe:
A. Observe the colour and identify the smell of the distillate.
B. Pour a small amount of the distillate on a watch glass, strike a match and bring
the flame close to the distillate. Does it catch fire? Write complete laboratory
report on this experiment and submit to your teacher.
Beer
The raw materials for beer are barley and hops. The first step is to bring the barley to ger-
mination whereby starch is converted into a type of sugar called malt sugar. Heat stops this
process and the material is now called malt. After drying and grinding the barley, water is
added in the mash tubes. After adding hops and yeast the process of fermentation begins.
Then it is stored in tanks for a period of time as required by a type of the product. Later it
is pasteurized and carbon dioxide is added under pressure and supplied to consumers. Al-
though the type of beers produced in the world are too many the average beer has alcohol
content between 2-6 per cent by volume.
Wine
Although various other fruits can be used, grapes are the most common raw materials for
producing wines. Grapes (or tether fruits) are first crushed and then steamed. The liquid
that is derived from the crushing process is called must. It then goes to a fermentation
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CHEMISTRY GRADE 12
takes place. The must then passes to a settling tank where sediment is allowed to settle,
and proceeds from there to a filter. The clear liquid is cooled in a refrigerator tank and it is
pasteurized as it passes through a flash pasteurizer. It finally goes to a storage tank where
it is kept for months or years. The older a wine is kept, the more mature it becomes and
usually is considered to have a higher quality fetching higher price. Most wines have an
alcohol content varying from 10-16 per cent by volume. Figure 3.16, presented a schematic
diagram which shows the major steps of Wine beverages.
Figure 3.16: schematic diagram which shows the major steps of Wine beverages
Liquor: Compared with beer and wine liquor contains a higher percentage of pure alcohol.
Normally fermentation stops by itself, if the alcohol concentration riches 15 to 17 percent
because yeast cells are not able to stay alive in alcohol of higher concentration.
To get drinks with higher concentration of alcohol the alcohol has to be separated from the
solution by distillation. Thus liquors (e.g. cognac) are made by distillation of grape wine;
rum is produced from sugar cane, and whisky from rye. Different types of liquors have
different alcohol concentration. Most of them however range between 30-45 percent of
alcohol by volume.
Local Preparation of Araki

Araki: Araki is the local Ethiopian alcohol which is prepared almost everywhere with cer-
tain local differences. In fact, the differences are in the ingredients and not in the process
of making it.
170
First, the barley is made into “Bikel” in the manner as was mentioned in the case of beer.
Then with the help of water the Bikel is mixed with Gesho (Rhamnuspronoides) powder
to make starter “Tinses”. The starter or “Tinses” is left to ferment for about four days. (It
may vary from place to place depending upon the local’s humidity and temperature). Then
the bread is baked from ingredients of Teff, Barley, Wheat, and Sorghum; depending upon
their availability and local preferences. The bread is broken down into small pieces and
mixed with the already prepared starter or “ Tinsis” and left to stand to ferment for a couple
of days ( 5 to 10 days). After it is fully fermented, a proportional amount of water is added
to liquidity the tick dough-like mixture and left for 1 to 2 days for further fermentation.
Finally, the liquid mixture is boiled and distilled following the traditional ways as depicted
in Figure 3.17. The distillate is called “Araki”. While the leftover residue or the un-distilled
component is locally called “ Atela” and it is usually used to feed cattle.
Figure 3.17: Preparation of Local Araki
Project 3.4
Do you know the raw materials that are used and the procedure to be followed to prapare
“Tella” or Bordie (depending your locality) a local non distilled alcohol in most of Ethiopi-
an homes? Please ask your parents and submit a report to your teacher?
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CHEMISTRY GRADE 12
3.4.9 Soaps and Detergents
Activity 3.21
Do you know any local industry in your surrounding that Manufactures soaps?
List them and discuss the raw materials that are used to manufacture soaps?
Soaps
Organic chemicals are used for the synthesis of soaps. For example, animal fat and vege-
table oils are used for manufacturing soap. Fats and oils are naturally occurring esters of
glycerol and the higher fatty acids. Soaps are substances used to remove dirt. They are also
called surfactants or surface-active agents. This is because they reduce the surface tension
of water and change the surface properties.
Soaps are either sodium or potassium salts of higher (long-chain) carboxylic acids. Soaps
that are sodium salts are called hard soaps and those that are potassium salts are soft soaps.
Soaps are prepared by boiling animal fat or vegetable oil with a base. The reaction that
produces soap is called saponification.
Example:
O
H2C O C C17H35
H2C OH
O
+ C17H35COO Na
+ 3NaOH HC OH
HC O C C17H35
Soap (sodium
O H2C OH octadecanoate)
H2C O C C17H35 Glycerol

Animal f at
The water-soluble group in ordinary soap (C17H35COONa) is – COONa and the fat-soluble
part is the chain of 17 carbon atoms, C17H35. It is represented in the structure below.
R C O Na
hydrophobic hydrophilic
long hydrocarbon chain (oil soluble) short ionic part (water soluble)
172
In industry, tallow, lard, cotton seed oil, palm oil, castor oil, olive oil, whale oil and the oil
of soybeans are used to prepare ordinary soap. When making hared soaps, the lye is usually
caustic soda, but when a soft soap is desired, caustic potash (KOH) and potassium carbon-
ate (K2CO3) are used and the glycerin is not salted out.
Industrially soap is produced in four basic steps:

Step 1. Saponification: A mixture of tallow (animal fat) and coconut oil is mixed with sodium
hydroxide and heated. The soap produced is the salt of a long chain carboxylic acid.
Step 2. Glycerine removal: Glycerine is more valuable than soap, so most of it is removed.
Some is left in the soap to help make it soft and smooth. Soap is not very soluble in salt
water, whereas glycerine is, so salt is added to the wet soap causing it to separate out
into soap and glycerine in salt water.
Step 3. Soap purification: Any remaining sodium hydroxide is neutralized with a weak acid
such as citric acid and two thirds of the remaining water removed.
Step 4. Finishing: Additives such as preservatives, colour and perfume are added and mixed in
with the soap and it is shaped into bars for sale. Figure 3.18 shows a flow chart that
showing the soap making process.
Figure 3.18: Flow chart showing the soap making process.
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CHEMISTRY GRADE 12
Experiment 3.6
Preparation of soap
Objective: to prepare soap from animal fat or vegetable oil.
Materials required: Animal fat or vegetable oil, NaOH, NaCl, measuring cylinder,
beaker, glass rod, Bunsen burner, filter paper, funnel, conical flask, and test tube
Procedure:
Measure 3 mL vegetable oil or 3 g animal fat and place it in a 100 mL beaker; add
3 mL of ethanol and 3 mL of 5M NaOH. Stir the mixture vigorously with a glass
rod and gently heat over a flame for 15 minutes or until it turns in to a paste. When
the paste begins to form, stir very carefully to prevent frothing. After all the paste
has formed, set the beaker on the bench to cool. Add about 15 mL of saturated NaCl
solution to the paste mixture and stir thoroughly. This process is called salting out
the soap. Filter off the soap mixture by suction filtration and wash the collected soap
precipitate with 15 mL of ice water.
A. Why do we add ethanol during the preparation?
B. What is the purpose of adding saturated NaCl solution to the paste mixture?
Write a lboratory report and present to the class
Detergents
These cleaning agents are often called, soap less soaps because they lather well, they are
very different from ordinary soaps in their chemical composition. Long open-chain alco-
hols and alkyl benzene sulphonic acid can be used for the production of detergents. Deter-
gents are sodium salts of sulphonated long chain organic alcohols.
R-C6 H4 SO3 Na, where:
R is an alkyl group with a chain of 10 to 18 carbon atoms. The water-soluble group is –SO-
3
Na while the fat soluble one is the –R -C6H4 groups.
The advantage of detergents is, that they lather well with both soft and hard water and even
with water that contains common salt or acids. They are more soluble than soap in water,
form stable emulsions with grease and do not form a scum with hard water because their
calcium and magnesium salts are soluble
One example of detergents is sodium lauryl sulfate, C12H25 — O — SO2 — ONa. It is pre-
pared first by reacting dodecyl (lauryl) alcohol with sulphuric acid followed by reaction
with sodium hydroxide. The reaction equation is:
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C12H25 OH + HO SO2 OH C12H25 O SO2 OH + H2O
Dodecyl alcohol Lauryl hydrogen

sulphate
H2SO4
(lauryl alcohol)
C12H25 O SO2 OH + NaOH C12H25 O SO2 ONa + HO

2
Sodium lauryl sulphate
Experiment 3.7
Investigating the Chemical Properties of Soap and Detergent
Objective: Describe the chemical properties of soap.
Chemicals: Soap produced in experiment 3.3, detergent
Equipment & Apparatus: Four 150 ml of beaker, cold water
Procedure
1. Weigh 3 g of your soap that you prepared in experiment 3.3 and 3 gram detergent
as directed by your teacher.
2. Add 3 gram of the soap you produced in experiment 3.3 in solution (3 mL distilled
water + 5 drops 3% magnesium chloride solution) in 150 ml of beaker labeled
soap then add 100 ml of water. Do the same thing for 3 gram of detergent in a 150
of beaker labeled. Detergent. Stir both beakers. Observe in which beaker leather
is well formed.
1. Based on your observation in procedure 3, which reagent (soap or detergent)
lathered well with hard water? Why?
Dry Cleaning
The qualities of some clothes decrease when they are washed with water using ordinary
soap. In order to avoid this, other chemicals are used for washing purposes that remove dirt
in the same manner as soaps. Dry cleaning refers to the use of different chemicals that are
capable of dissolving grease and other dirt stains in a similar manner as soaps without the
use of water. The most commonly used chemicals in dry cleaning are organic chemicals
such as tetra chloromethane, CCl4; tetra chloroethylene, Cl2C = CCl2; benzene and gasoline.
For example, Silk will turn yellow if it is treated with strong soap during laundering. Often
the instruction for cleaning clothes contains the sentence: Use only lukewarm water for
cleaning. Otherwise the quality of the product will decrease. Because natural fibers are
mostly mixed with artificial ones, laundering should not be applied. Instead of laundering,
dry cleaning is applied. To dry clean, means to use different chemical those are able to dis-
solve grease and stains in a similar manner as soaps, the only difference being that contact
with water is avoided.
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CHEMISTRY GRADE 12
Project 3.5
Presently soap is prepared in small scale (in cottage industry) in most of Ethiopian cities
and become a means of income generating? Do you know the raw materials that are used
and the procedure to be followed to prepare the soap in such cottage industry? Please visit
the nearby cottage industry and submit a report to your teacher?
Exercise 3.12
Do the following questions individually.
1. Explain the difference between chemical and mechanical pulping.
2. How does natural tanning differ from mineral tanning?
3. Describe the modern methods of food preservation.
4. Explain the reason how the paper quality produced in industries differs.
5. What are the common chemicals that are used for mineral tanning?
6. What is the mechanism that makes food to be preserved for a long time
without spoil?
7. How does the traditional way of preparation of Araki differ from industrially
liquor (Gin)?
8. List the raw materials to produce “Tej”.
9. Explain the difference between hard soap that is used for a cleaning of our
clothes and the soft soap that used for our body hygiene.
10. How do soap and detergent act on dirt particles during the process of
cleaning?
11. Describe how detergent is more effective in hard water compared to soaps.
and write the reaction equation that takes place during the cleaning action?
Unit Summary
~ Before 19th century, chemistry and chemical technology were devoted to satis-
fying the needs of everyday life however the methods of production used were
manual and small scale.
~ In the 19th century as a result of Industrial revolution the chemical industries
began to develop at a very high rate. The demands for goods produced through
chemical processes increased.
~ Ethiopia, as developing country, will find chemistry and chemical technology
very important components of economic growth and development.
~ Industrial chemistry as the branch of chemistry which applies physical and
chemical procedures towards the transformation of natural raw materials and
their derivatives to products those are of benefit to humanity.
~ The resources that can be replenished through rapid natural cycles are known
as renewable resource. Examples: plants, (crops and forests), and animals
176
~ The resources that cannot be replenished through natural processes are known
as non-renewable resource. Examples: fossil fuels and, minerals.
~ Ammonia is an important compound, essential to man for a variety of di-
verse uses. It is used as a fertilizer, cleaning agent, antimicrobial agent, etc. the
process that used to manufactured ammonia in industries are called Haber -
Bosch process
~ Nitric Acid is a highly corrosive mineral acid. And it is a strong oxidizing agent
and it is produced industrially from ammonia by the three-step Ostwald pro-
cess.
~ The largest percentage of nitric acid is used to synthesize ammonium nitrate, a
water-soluble fertilizer. Large quantities are also used to make plastics, drugs,
and explosives such as trinitrotoluene (TNT) and nitro glycerin.
~ H2SO4the largest volume chemical produced in the world and rate of consump-
tion of this acid is considered as a measure of a country’s industrialization.
~ Most of the sulphuric produced in the world is manufactured industrially by
the contact Process which involves four major steps. Sulfuric is used in the
production of fertilizers, detergents, plastics, paints, explosives, as electrolyte in
car batteries and as a catalyst in the manufacture of many chemicals.
~ DAP has the advantage of having both nitrogen and phosphorus, which are
essential for plant growth.
~ The most common forms of N fertilizer include anhydrous ammonia, urea, and
urea-ammonium nitrate (UAN) solutions.
~ Urea is a solid fertilizer with high N content (46%) that can be easily applied to
many types of crops and turf. It is manufactured by reacting CO2 with NH3 .
~ Pesticides belong to a category of chemicals used worldwide to prevent or con-
trol pests, diseases, weeds and other plant pathogens in an effort to reduce or
eliminate yield losses and maintain high product quality. Examples of common
pesticides oregano-chlorine, oregano-phosphate and carbamates.
~ An herbicide is a chemical used to kill or otherwise manage certain species of

plants considered to be pests. Examples: chlorophenoxy acids such as 2,4-D
and 2,4,5-T; triazines such as atrazine, hexazinone, and simazine.
~ Sodium carbonate (washing soda) is a white crystalline solid. It exists as a

decahydrate (Na2CO3. 10H2O) compound. Sodium carbonate is manufactured
by Solvay process in industrial scale and has industrial and domestic uses.
~ NaOH has been manufactured at large scale for many years from readily ob-
tainable raw materials i.e. Rock salt “NaCl” sodium chloride & water “H2O.
~ Sodium hydroxide is used in numerous industrial processes such as in pulp
and paper manufacturing, alumina extraction from bauxite in aluminum pro-
duction, as well as in the textiles industry and drinking water production.
~ The chemical/manufacturing industry in Ethiopia produces basic chemicals
based on local raw materials and currently there are a total of 153 chemical and
chemical-related product manufacturers according to CSA’s raw data for the
year 2014.
~ Glass is an amorphous or non-crystalline solid material and is such a popular
material in our homes because it has all kinds of really useful properties. Al-
most all glass contains silica as the main component.
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CHEMISTRY GRADE 12
~ Soda-lime glass is ordinary glass which is a mixture of sodium silicate and

calcium silicate.
~ Traditional ceramics, such as porcelain, tiles and pottery are formed from
minerals such as clay, talc and feldspar whereas industrial ceramics, however,
are formed from extremely pure powders of specialty chemicals, such as silicon
carbide, alumina, barium titanate, and titanium carbide.
~ Ethiopia has a huge amount of reserve of raw materials for the production of
cement. The major raw materials for the production of cement are limestone,
clay, silica sand, gypsum, and pumice.
~ Sugar is mainly manufactured from a raw material sugar cane with 8 stage in-
dustrial process starting from collecting the Harvest of sugar cane to for grind-
ing to the last stage separation and packaging
~ Paper is a mixture made from rags and wood pulp glued together with some
additions, bleached and dried.
~ Tanning is a process of converting raw animal hides and skin to leather, using
tannin. Leather is a durable and flexible material created by the tanning of
animal hides and skin.
~ Food preservation usually involves preventing the growth of bacteria, fungi
and other microorganisms, as well as reducing the oxidation of fats, which
causes rancidity.
~ The most common modern methods of food preservation are freezing, vacu-
um-packing and Freeze-drying
~ The alcohol, which is the constituent of beverages, is known as ethyl alcohol or
ethanol.
~ The preparation of ethyl alcohol is atypical chemical process. It can be done
from sugar by bacteria, without air (oxygen).
zymase
C6 H12O6 → 2C2 H 5OH + CO2
bacteria
~ The common alcoholic beverages in Ethiopia Beer, liquor (Araki), Wine, Tej
and Tella
~ There are many kinds of soap available on the market, but the methods used in
making them are similar. It is expressed in the equation: Long chain fatty acids
(Fat) + NaOH (Lye) → Soap + Glycerin represents the changes in practically
all soap making. The soap making process is called saponification.
178
Check List
Key terms of unit 3
 Alcoholic Beverages  Haber - Bosch process  Paper and Pulp
 Araki  Herbicides  Pesticides
 ceramics  Industrial chemistry  Renewable resources
manufacturing  Le Chatelier’s  setting of cement
 Chemical industry principle  soaps and detergents
 Contact process  Nitrogen Based  Solvay process
 DAP Fertilizers  sugar manufacturing
 Dry Detergents  Non-Renewable  Tannery
 Food Preservation Resources  Urea
 glass manufacturing  Ostwald Process  Valuable products

Part I. Write True if the statement is true and false if the statement is false
1. In early stage of industrial chemistry, the methods of production used were manual
and small scale.
2. Minerals like Co, Au, Fe and Pb are renewable?
3. The largest percentage of nitric acid is used to synthesize ammonium nitrate, a water-soluble
fertilizer.
4. H2SO4 is a leading economic indicator of the strength of many industrialized nations.
5. Diammonium monohydrogen phosphate (DAP) is a white crystalline compound that
is insoluble in water
6. In Ethiopia’s manufacturing/chemical industry is still at a nascent stage.
7. The present-day paper is not completely different from the old papyrus which was
used centuries ago.
Part II: Choose the best answer for the following questions among the given alternatives
1. One of the following is class of manufacturing industries based on the product/goods

they manufactured?
A. Food, beverages and tobacco industries
B. Paper products, printing and publishing
C. Textiles, wearing apparel, leather goods
D. All of the above
2. One of the following is not the properties of nitric acid
A. It is a strong acid and dissociates completely to give H3O+ and NO3–
B. It is a highly corrosive mineral acid
C. It is a strong reducing agent
D. Nitric acid forms a large number of salts which is soluble in water
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CHEMISTRY GRADE 12
3. From the following one is not the properties of sulphuric acid

A. It has an appearance similar to that of water
B. The dissolution of sulfuric acid in water is endothermic
C. Pure H2SO4 melts at 10.5°C and boils at 338°C
D. It is corrosive to the skin and is a strong oxidizing agent
4. Name the catalyst used in the Contact process.
A. Finely-divided Iron C. Nickel
B. Vanadium (V) Oxide D. Chromium
5. What are the conditions used in the Contact process?
A. 1 atm & 450°C C. 200atm & 450°C
B. 450 atm & 1°C D. 450atm & 200°C
6. What is H2S2O7?
A. Concentrated sulfuric acid C. Oleum
B. Sulfur trioxide D. Hydrogen sulfate
7. What are the uses of sulfuric acid?
A. In the manufacture of detergents and fertilizers
B. As food preservative
C. As a battery acid
D. As a bleach
E. A and C
8. In the Contact process, what happens to the equilibrium when the pressure is in-
creased?
A. Shifts to the left C. No change in equilibrium
B. Shifts to the right D. None
9. What is the name of manufacturing process of sulfuric acid?
A. Contact C. Haber
B. Frasch D. Ostwald
10. 2 SO2 ( g ) + O2 ( g )  2 SO3 ( g )
The equation above refers to the 2nd stage of Contact Process. What are the optimum
conditions to favour the yield of sulfur trioxide?
A. Low Pressure D. High Temperature
B. High Pressure E. B&C
C. Low Temperature
11. Process in which sodium carbonate is manufactured is called
A. calcination C. solvay process
B. metallurgy D. carbonation
12. Pick out the wrong statement?
A. High early strength cements are made from materials having high silica to
lime ratio
B. The function of gypsum in cement is to enhance its initial setting rate
C. Acid resistant cements are known as silicate cement
D. Major component of greyish Portland cement is tricalcium silicate
13. Among the following compounds which one is recycled in Solvay process during the
‘ production of Na2CO3
180
A. NaCl D. CaCO3
B. CO2 E. B and C
C. NH3
14. The last step of the Solvay process is
A. preparation of ammonical brine
B. carbonation
C. preparation of carbon dioxide and slaked lime
D. recovery of ammonia
15. The third step of the Solvay process is
A. preparation of ammonical brine C. filtration
B. carbonation D. calcination
16. One of the following is the most common nitrogen based fertilizers
A. Anhydrous ammonia
B. Urea
C. urea-ammonium nitrate (UAN) solutions
D. all
17. One of the following is the most important chemical groups of herbicides?
A. chlorophenoxy acids such as 2, 4-D
B. organic phosphorus chemicals such as glyphosate;
C. amides such as alachlor and metolachlor
D. all of the above
18. Basic chemicals or manufacturing product produced in Ethiopia from the local raw
materials available
A. Sugar D. caustic soda
B. Cement E. All of the above
C. soaps and detergent
19. The product obtained by combining a material rich in lime, CaO with other materi-
als such as clay, which contains silica, SiO2, along with oxides of aluminum, iron and
magnesium is:
A. Glass C. Steel
B. Cement D. Fertilizer
20. Which of the following is not a specific characteristic of chemical industries?
A. using naturally available raw materials
B. providing transport services to customers
C. involving chemical reactions
D. consuming energy
21. Which of the following is a non-renewable resource?
A. soil C. water
B. petroleum D. plants
22. In the tanning process, the purpose of putting the skin into slaked lime solution is to:
A. facilitate the removal of unwanted flesh
B. dehydrate the skin
C. facilitate the removal of hair
D. Soften the skin
23. The stage in which the shredded sugarcane travels on the conveyor belt through a
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CHEMISTRY GRADE 12
series of heavy-duty rollers, which extract juice from the pulp in sugar manufacturing
is called.
A. Juicing C. Cleansing and Grinding
B. Collecting the Harvest D. Clarifying
24. Preservation usually involves preventing _____________________
A. The growth of bacteria
B. The growth of fungi and other microorganisms,
C. Reducing the oxidation of fats, which causes rancidity?
D. All of the above
25. ___________ is a component to make soft soap along with the vegetable oil or animal
fat
A. Caustic soda C. K2CO3
B. Caustic potash (KOH) D. B and C
Part III: Give Short Answer for the following Questions
1. Give a reason why among the essential aspects of industrial chemistry, the chemical
industry is the prominent one?
2. Write the chemical equation which shows the three major steps of NH3 production.
3. List the common uses of H2SO4.
4. What is the basic difference in the composition of glass and cement?
5. What is ceramics?
6. Write the main chemical equations involved in the production of cement.
7. Describe the refinery processes involved in sugar production
8. Write the key reaction during the Solvay process? And please describe how solid
9. NaHCO3 is formed.
10. What is the positive aspect of the application of pesticides?
11. Describe the process of production of the most local alcoholic beverages in Ethiopia.
12. Describe the cleaning action of soap and dry detergent.
182
POLYMER
UNIT 4
POLYMER
H
H
H
H
H
H
H
H
H
H
H
H
n
H
H
H
Unit Outcomes
At the end of this unit, you will be able to

 define polymers
 realize that most of the materials around you may be polymers
 define, identify and classify monomers
 list a variety of synthetic polymers & natural polymers & explain their
differences
 classify polymers into their types based on different criterion
 classify synthetic polymers as addition or condensation polymers &
identify their monomers;
 classify synthetic polymers as addition or condensation polymers &
identify their monomers
 describe the properties of the different types of polymers
 describe the monomers, properties & uses of plastics, rubbers,
carbohydrates & proteins;
 list the applications of the different types of polymers
 define polymerization reactions
 list the different types of polymerization reactions
 describe the process of addition & condensation polymerization;
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CHEMISTRY GRADE 12
4.1 Introduction to polymers

 define the term monomer
 define the term polymer
 identify material with polymeric nature
Activity 4.1
1. With your friends at your bench, look at
 the textile fibre of your clothes
 your hair and skin
 the wood from which your desk is made
 the glass of the window
2. and identify the common characteristics of these materials. Set criteria
and categorize them.
Polymer
The word polymer is derived from the Greek words’ ‘poly’ meaning many and ‘meros’
meaning part. It follows that this term applies to giant molecules built up of large numbers
of interconnected repeating units. A polymer is a large chainlike molecule built up from
many repeating smaller molecules.
A polymer is generally comprised of more than 100 monomers; structures with lower
numbers of monomers are known as oligomers. These polymers or oligomers may be linear,
slightly branched, or highly interconnected. In the branched case the structure develops into
a large three-dimensional network. With few exceptions, the repeat unit in the polymer
usually corresponds to the monomer from which the polymer was made. The size of a
polymer molecule may be defined either by its mass or by the number of repeat units in
the molecule. This latter indicator of size is called the degree of polymerisation, DP. The
relative molar mass of the polymer is thus the product of the relative molar mass of the
repeat unit and the DP.
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POLYMER
Example 4.1
Examples of polymers are:
• polyethylene,
• wood (cellulose),
• protein and
• quartz
Monomers
The small molecules used as the basic building blocks for polymers are known as monomers.
Mono means one.
Example 4.2
Example for monomers are:
• Glucose(C6H12O6) a monomer for cellulose (wood)
• ethylene a monomer for Polyethylene
• amino acid (NH2CH(R)(COOH)) a monomer for protein,
• Silicon dioxide (SiO2) commonly silica is a monomer for Quartz (sand)
4.2 Classification of Polymers

 categorize a given polymer based on different criteria;
 identify natural and synthetic polymers;
 tell the monomer of natural rubber;
 list the properties and applications of natural and synthetic polymers;
 draw the structures of disaccharides;
 describe polysaccharides;
 draw the structure of starch and cellulose;
 draw the structure of polyethylene, polypropylene, polyvinylchloride,
polytetrafluoro ethylene and polymethyl methyl methocrylate
 give examples polypropylene, polyvinyl chloride and polyethylene
products
Activity 4.2
Within your group, discuss the causes of the differences between different
types of polymers.
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CHEMISTRY GRADE 12
There are a number of methods of classifying polymers. A few of the methods of polymers
classification are listed below.
A polymer might be made from identical or different types of monomers. This could be
used to classify polymers as homopolymers or copolymers.
Homopolymers
Homopolymers are those made from only one type of monomer. For example, polyethylene
is synthesized by the polymerization of one type monomer, ethene (ethylene).
n CH Catalyst CH2 CH2 n

2 CH2
Polyethylene
Ethene (ethylene)
(monomer)
(homopolymer)
Copolymers
Activity 4.3
With your discussion group, identify the challenges arise when different types
of monomers are used to synthesize a polymer with specific properties such as
melting point, density etc.
Copolymers are those prepared by polymerizing more than one kind of monomer unit.
For instance, ethene (H2C=CH2) and propene (H2C=CH–CH3) can be copolymerized to
produce a polymer that has two kinds of repeating units:
CH3
Catalyst
n CH
2 CH2 + m CH2 CH CH3 CH2 CH2 n CH2 CH m
monomer monomer copolymer
Copolymers are classified as random or regular, based on the way the monomers are
arranged along the polymer chain (Figure 4.1).
Random polymers contain repeating units arranged in a random fashion.
Regular polymers contain a sequence of monomers in regular alternating repeating units.
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POLYMER
A B B A A A B A A Random copolymer
A B A B A B A B A Regular copolymer
Figure 4.1: Random and Regular copolymers (Where, A and B represent monomer units).
Another classification system of polymers is based on the nature of the chemical reactions
employed in the polymerisation. Here the two major groups are the condensation and the
addition polymers.
Condensation polymers are those prepared from monomers where reaction is accompanied
by the loss of a small molecule, usually of water, for example polyesters which are formed
by the condensation shown in the reaction:
O
n HO R OH + n HOOC R' COOH HO R COO R' COO n + (n-1) H2
By contrast, addition polymers are those formed by the addition reaction of an unsaturated
monomer, such as takes place in the polymerisation of vinyl chloride:
n CH CHCl CH2 CHCl n

2
Furthermore, polymers can be classified based on whether they are naturally occurring or
made by man (synthetic).
Natural polymers
Activity 4.4
Discuss with your friends on:
1. the similarity between starch and cellulose
2. the difference between starch and cellulose
3. the properties of natural rubber
4. similarity between wood and cotton.
the nature of your genetic material and present your answer to the class.
Natural polymers occur in nature and can be extracted, and often referred to as biopolymers.
Common natural polymers include macromolecules such as polysaccharides (e.g., starches,
sugars, cellulose, gums, etc.), proteins (e.g., enzymes), fibbers (e.g., wool, silk, cotton),
polyisoprenes (e.g., natural rubber), and nucleic acids (e.g., RNA, DNA) (Figure 4.2).
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CHEMISTRY GRADE 12
CH2OH CH2OH CH2OH

O O O
OH OH
OH
O O OH
OH OH
OH OH
300-600
Starch
OH CH2OH OH
OH CH2OH
O OH
OH OH O O
OH OH
O O
O O
CH2OH CH2OH n
OH OH
Cellulose (cotton, wood etc)
H H O H H O H H O H3C H
N C C N C C N C C C C
* C H2C *
R1 R2 R3 H2 n
Protein (Skin, hair, muscles etc.) Natural rubber
O PO H H O
O N
N N OH
O N H N
O N O O
N
H H O N O PO
O O N O O
O P N N
O N H N
O N O
N O
O H H O
P O
O H O
O H N N
O P O N
O N O
O N H N
N O
H P O
O O O
O O O HN
P O N N N
O NH O
O H O O
N N N
O P
H O O
HO
A portion of Deoxyribose nucleic acid (DNA)
Figures 4.2: Some natural polymers
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POLYMER
Synthetic polymers
Activity 4.5
Discuss on the following questions in groups and present your answer to the
class.
1. List any material around you and identify those with polymeric nature.
2. Identify those polymers which are manmade.
Synthetic polymers are those which are human-made polymers. Synthetic polymers are
sometimes referred as “plastics”, of which the well-known ones is polyethylene (Figure
4.3). It has no taste or odour and is lightweight, nontoxic and relatively cheap.
H H H H H H H H
C C C C C C C C
H H H H H H H H
n
Figure 4.3 Structure of polyethylene (polyethene)
Some of its primarily uses are in making squeeze bottles, plastic wrapping, garment bags,
trash bags and electrical insulation (Figure 4.4).
Polyethylene trash bags Squeeze bottle (Wash bottle) Polyethylene tube
Figure 4.4: Some polyethylene materials
Polypropylene
The monomer of polypropylene is propylene (propene) (CH2=CHCH3). It is produced by
the addition polymerization of propylene.
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CHEMISTRY GRADE 12
H H H H H H H H
C C C C C C C C
H CH3 H CH3 H CH3 H CH3

n
Figure 4.5: Structure of polypropylene
Polypropylene is stronger than polyethylene. It is used for making food containers that can
safely be washed in a dishwasher. It can also be used for making ropes; fishing nets, carpets,
and bottles (Figure 4.6).
Polypropylene rope Polypropylene carpet Polypropylene bottles
Figure 4.6 Some polypropylene products
Polyvinyl Chloride (PVC)

Polyvinyl chloride is the third most widely produced plastic, after polyethylene and
polypropylene. It is prepared by the polymerization of vinyl chloride.
H Cl
C C
H CH 3
n
Figure 4.7: Structure of polyvinyl chloride
It is commonly used for making pipes, leather-like materials, shoes, raincoats, aprons,
wallpaper, floor tile, and phonograph records.
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POLYMER
PVC pipes PVC floor tile PVC raincoat
Figure 4.8: Some polyvinyl chloride products.
Polymethyl methacrylate (Perspex)

Polymethyl methacrylate, PMMA, is sold under the trade name Lucite or plexiglass. It is
prepared by the polymerization of methyl methacrylate (CH2=C(CH3) COOCH3.
CH3
CH2 C
COOCH3 n
Figure 4.9: Structure of Polymethyl methacrylate
PMMA is a lightweight glass-like polymer used as a glass substitute for example, in airplane
windows and streetlights.
Polytetrafluoroethylene, PTFE, Teflon

Teflon is prepared by the addition polymerization of tetrafluoroethylene (CF2=CF2).
Teflon has good resistance to chemical attack, and it can be used at any temperature between
–73 °C and 260 °C with no effect on its properties.
F F
C C
F F
n
Figure 4.10: Structure of Polytetrafluoroethylene (PTFE)
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CHEMISTRY GRADE 12
It also has a very low coefficient of friction, which makes it waxy or slippery to touch. As a
result, it is particularly suited to applications in food preparation. For example, bread dough
does not stick to a Teflon-coated surface. Teflon is used for coating cooking utensils and for
making electrical insulation (Figure 4.11).
Teflon coated dish Teflon tape

Figure 4.11: Some Teflon materials
One way of classification of polymers is to adopt the approach of using their response to
thermal treatment and to divide them into thermoplastics and thermosets.
Thermoplastic polymers
Activity 4.6
Discuss in groups and present your answer to the class. Describe what happens
to wood, nylon, polyethylene, and hair when they are subjected to heat.
Thermoplastic polymers are those which melt when heated and resolidify when cooled.
They are comprised of essentially linear or lightly branched polymer molecules. They can
be remelted or reprocessed (recycled).
Examples of thermoplastics include: polyethylene, polypropylene, polyvinyl chloride,
teflon, polymethyl methacrylate, nylon and polyester (Dacron), polystyrene (Rubber),
polyamide, Polyvinyl Chloride (PVC).
Thermoset polymers
Thermoset polymers are those which do not melt when heated, but at sufficiently high
temperatures, decompose irreversibly. They are substantially cross-linked materials,
consisting of an extensive three-dimensional network of covalent chemical bonding. They
exhibit resistance to heat, corrosion, and mechanical stress. Thermoset materials are no-
recyclable.
Examples thermoset polymers include: Bakelite, cyanate esters, epoxy resin, fibber glass
(a fibber-reinforced thermoset), polyester resin, Polyurethane, Silicone resin, Vinyl esters,
Vulcanized rubber.
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POLYMER
Exercise 4.1
1. Define each of the following terms:
a. monomer e. copolymer
b. polymer f. natural polymer
c. homopolymer g. synthetic polyme
2. What are some of the polymers that you encounter every day? Describe
their physical properties.
3. Why do different polymers have different properties?
4. Which of the materials listed below may not be made of polymers? leather,
computer key board, automobile body, cup, rubber, meat, mirror, plastic
chairs
5. Classify each of the following polymers as natural or synthetic
a. Wool d. Teflon g. Bakelite

b. Dacron e. Cellulose h. Glycogen
c. Insulin f. Polyvinyl chloride j. DNA
3. Explain the difference between thermoplastics and thermosetting polymers,
using examples.
4. What makes thermoplastic materials recyclable, whereas thermosetting
ones are not?
5. List some thermoplastic polymers and describe their properties with the
corresponding applications.
6. List some thermoset polymers and describe their properties and applications.
4.3 Polymerization Reactions

After completing this subtopic, you will be able to
 describe polymerization reaction
 list the types of polymerization reactions
 give examples of addition polymers;
 explain common uses of addition polymers;
 give examples of condensation polymers;
 explain the uses of these condensation polymers: nylon, polyester and
Bakelite
 list the steps in addition polymerization
 identify whether a given monomer undergoes addition or condensation
polymerization
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CHEMISTRY GRADE 12
Activity 4.7
Discuss in groups and present your answer to the class.
1. Recall the types of reactions you have learned so far in organic chemistry
and explain the Characteristics and conditions under which these reactions
take place?
2. List the functional groups that may serve for polymerization.
The chemical change by which monomer units combine to form a polymer is known
as polymerisation reaction. The essential feature of a monomer is to have two or more
functional groups (polyfunctionality). This gives each monomer the capacity to form
chemical bonds to at least two other monomer molecules.
Bifunctional monomers can form only linear, chainlike polymers. Monomers with higher
functionality yield cross-linked, network polymeric products.
Addition Polymerization
Addition polymerization is a reaction in which a chain reaction adds new monomer units to
the growing polymer molecule one at a time. This type of polymerization is also known as
chain-growth polymerization.
This type of polymerisation reaction occurs by those involving unsaturated monomers. For
example, the addition polymerization of many ethylene molecules yields polyethylene and
that of styrene molecules gives polystyrene.
H H
H H
Catalyst
n C C C C
H H H H n
Ethylene (ethene) Polyethylene
HC CH CH2 n
CH2
n Catalyst
Styrene Polystyrene
Note that the molecular formula of a polymer is n times that of the monomer and upon
polymerization, the double bond is converted to a single bond. When monomers with triple
bonds are used it is converted to double bonds.
Note also that: If a polymer is given, you can identify the monomer unit that is repeated
in it.
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POLYMER
If the mass of the polymer is known, the number of the monomer molecules is determined
by dividing the mass of the polymer by the molar mass of the monomer.
Example 4.3
The addition polymer polyvinyl chloride (PVC) has the structure
H H H H H H
C C C C C C
H Cl H Cl H Cl
A) Draw the structure of the monomer from which PVC is made
B) How many monomer units are in a PVC polymer that has a molar mass of
1.33 x 105 g/mole
Solution
A) We need to find the repeating unit from which this polymer chain is
constructed
H H H H H H
C C C C C C
H Cl H Cl H Cl
H H
The repeating unit C C and the monomer have carbon-carbon

double bond.
H Cl
B) If the PVC had a molar mass of 1.33 × 105 g/mol, how many monomer units
(n) are there?
Given: Molecular mass of CH2=CHCl (Venyl chloride) is 63.5g/mol
Mass of the PVC 1.33 × 105 g/mol
Required: The number (n) of CH2=CHCl
Relation:
Molar mass of the polymer
Number of monomer units ( n ) =
Molar mass of the monomer
1.33 × 105 g / mol
=
62.5g / mol
= 2128 vinyl chloride molecules
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CHEMISTRY GRADE 12
Steps of addition polymerization

The addition polymerization process takes place in three distinct steps.
1. Chain initiation step: it is a time when the polymerization process is started by means
of a reactive initiator molecule. The initiator molecules can be a free radical, a cation or
anion. These reactive centres react readily with other monomers without eliminating
the active centre.
2. Chain propagation step: It is the period when a monomer adds to the growing chain,
with the free radical, cation or anioin transferring to the chain end. High molar mass
polymers are formed right from the beginning of the reaction.
3. Chain termination step: This is the step when the polymerization is stopped since chain
reactions do not continue indefinitely. The radical, cation, or anion is “neutralized”
stopping the chain propagation.
A polymerization reaction initiated by free radicals is called a free radical

polymerization. The free-radical route to chain polymerisation is the most important
step in polymerization reaction.
A polymerization reaction initiated by a cation is called a cationic polymerization.
A polymerization reaction initiated by an anion is called an anionic polymerization.
Example 4.4
Example for Free radical polymerization
1. Chain initiation:
The free radical on the initiator fragment, shown: as Ra∙, attacks the covalent π
bond in the monomer, leaving a free radical on the monomer
Ra + CH2 CH2 Ra CH2 CH2
initiator monomer monomer (f ree radical)
(molecule)
2. Chain propagation
CH2 CH2 + CH2 CH2 CH2 CH2 CH2 CH2
3. Chain termination
Termination is achieved in two possible processes.
a) A free radical is destroyed by the combination reaction when two chains link
as
CH2 CH2 + CH2 CH2 CH2 CH2 CH2 CH2
b) chain transfer may occur to continue polymerization of another chain
+ H HC CH + H
CH 2CH 2 2 2 3
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POLYMER
Polymers include polyethylene, polyvinyl chloride, acrylics, polystyrene, and

polyoxymethylene (acetal) are made by addition polymerization (Equation 4.12).
H R1 H R2
H R1 H R2
+ C C C C
n C C m C C
H H H H H H H H
n+m
Exercise 4.2
1. List the types of polymerization reactions.
2. Define each of the types of polymerization reactions.
3. Show the steps followed in the polymerization of styrene to polystyrene.
Describe each step.
Condensation polymerization
Condensation polymerization involves the combination of monomer molecules, with the
release of simple molecules like water or methanol as by product. These products are
normally referred to as condensate. This polymerization is also known as step growth
polymerization. In order to produce a condensation polymer, the monomers involved two or
more functional groups. Typically, such reactions take place between reactive components,
such as dibasic acids with diamines to give polyamides, or dibasic acids with diols to form
polyesters. Proteins, starch and cellulose are examples of natural condensation polymers.
Whereas, Polyester (Polyethylene terephthalate or Dacron) and the polyamide Nylon 66
represented below, are two examples of synthetic condensation polymers.
They can be produced by the condensation reaction of diacids and diamines. One of the
most common polyamides is nylon 66 or nylon. It is a copolymer and is prepared by the
condensation of 1, 6-diaminohexane (hexamethylene diamine) and 1,6-hexanedioic acid
(adipic acid). The basic amine reacts with the acid to form a salt. Heating removes water
and forms the amide bonds.
Dacron is a copolymer and is formed when equimolar amounts of 1, 4-benzene dicarboxylic

acid (terephthalic acid) and 1, 2-ethanediol (ethylene glycol) react.
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CHEMISTRY GRADE 12
O O
n HO C C OH + n HO CH2CH2 OH
Ethylene glycol
Terephthalic acid Heat
O O
HO C C O CH2CH2 OH + (2n - 1) H2O

n
Polyethylene terephthalate (PTE)
O O
n HO C C OH + n HN (CH2)6 NH2
(CH2)4 2
Adipic acid Hexamethylene diamine
Heat
O O
n HO C C NH NH + (2n - 1) H2O
(CH2)4 (CH2)6 nH
Nylon 66 (the numbers indicate there are six carbon atoms each in hexamethylene diamine
and adipic acid)
Dacron is a strong and impact resistant. It is colourless and has high transparency. It is
mainly used for synthetic fibbers. Mixing with various amounts of cotton it gives fabrics
that are durable, easily dyed and crease-resistant. It is also used for making bottles and
packaging materials.
Uses of nylon include making parachutes, ropes, clothes, stockings, hair combs, and rugs.
They are also used to reinforce automobiles tires.
Consider the reaction between an alcohol with two –OH groups, HO–R –OH, and
a dicarboxylic acid, HOOC–R–COOH as represented below. In this case the ester formed
still has a reactive group at both ends of the molecule.
198
POLYMER
H2O
HO R O H + HO C R C OH HO R O C R C OH + H2O
O O
O O
Dihydroxy alcohol Dicarboxylic acid Ester with active
end groups
The general structure of the polyester can be represented as
' '
C R C O R O C R C O R O
O O O O
Section of the polyester
Experiment 4.1
Synthesis of Nylon
Objective: To prepare nylon and study its properties.
Apparatus and Chemicals: 250 ml beakers, dropping funnel, glass rod, forceps or
copper wire hooks, 0.5 M basic solution of hexamethylenediamine, 0.5 M NaOH
solution and adipoyl chloride.
Caution: Wear gloves while doing this experiment.
Procedure:
1. Place 5 mL of Solution A in a small beaker. Solution A: Prepare a 0.5 M basic
solution of hexamethylenediamine (or 2,6 – diaminohexane, H2N(CH2) 6(NH2)
as follows: weigh 6 g of hexamethylene diamine in a large beaker and dilute to
100 mL with 0.5 M NaOH solution.
2. Place 5 mL of Solution B in a second beaker. Solution B: Weigh 5 g of adipoyl
chloride and dissolve in 100 mL of cyclohexane.
3. Slowly add solution B to solution A using dropping funnel, pouring it down the
side of the slanted beaker. Do not stirr the mixture of solution A and solution B.
4. 4. Nylon will form at the interface of the two solutions.
5. Draw a thread out of the interface using forceps or a copper wire hook, and draw
the thread out of the beaker using glass rod as a pool and slowly windup the
thread as you draw it out.
6. After nylon has been collected, wash it thoroughly with water, dry it superficial-
ly with towel then let it dry.
Observation and discussion
A. Why the two solutions are not able to mix?
B. Why is adipoyl chloride used instead of adipic acid?
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CHEMISTRY GRADE 12
Exercise 4.3
1. Determine the monomers used to prepare
a. –[OC-C 6H 4-COO-(CH 2)2-O]- n
b. –[NH=CH 2-CO-N-CH 2-CO]- n
c. Decide the type of polymerization reaction taking place between
the monomers H2NCH 2(CH 2) 4CH 2NH 2 COClCH 2(CH 2)6CH 2COCl.
Write the structure of the polymer.
2. Consider a polymer made from tetrachloroethylene.
a. Draw a portion of the polymer chain.
b. What is the molar mass of the polymer if it contains 3.2 × 103
tetrachloroethylene?
c. Calculate the percentage of C and Cl in the polymer?
3. Write the structure of the following polymers and also indicate the monomer
units involved in the formation of these polymers.
d. Nylon 66 b. Dacron
4. Describe the major uses of nylons and polyethylene terephthalate.
Unit summary
~ A polymer is a large molecule built up from numerous smaller molecules. These
large molecules may be linear, slightly branched, or highly interconnected.
~ The small molecules used as the basic building blocks for these large molecules are
known as monomers.
~ The size of a polymer molecule may be defined either by its mass or by the number
of repeat units in the molecule.
~ There are a number of methods of classifying polymers. These include
o based on whether they are naturally occurring or made by man (synthetic).
o using the types of monomers used to make the polymer to classify as
homopolymers or copolymers.
o their response to thermal treatment and to divide them into thermoplastics and
thermosets
o based on the nature of the chemical reactions employed in the polymerisation
and to divide into condensation and addition polymers.
~ Each of the following polymers are made by addition polymerization. ‹
o Polyethylene ‹
o Polypropylene
o Polyvinyl chloride (PVC)
o Polymethyl methacrylate (PMMA) ‹
o Teflon ‹
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POLYMER
o Polystyrene ‹
o Natural rubber
~ Polymers that are synthesized by condensation polymerization are. ‹
o Nylons ‹
o Polyesters ‹
o Bakelite ‹
o Carbohydrates, and ‹
o Proteins‹
~ Thermoplastics soften on heating and can be molded into different shapes,
and the process of heating and cooling can be repeated several times, but once
thermosetting plastics are solidified, they cannot be softened or remolded on
heating.
~ The uses of polymers include
o in biology: the construction of structures, energy generation, physiological
processing.
o synthetic fibbers,
o building materials
o cooking utensils
o ropes, carets, bottles, etc.
Check List
 Addition  Monosaccharides  Polyvinyl chloride
polymerization  Natural polymer (PVC)
 Butyl rubber  Natural rubber  propylene
 Catalyst  Nylon  Repeating unit
 Copolymer  Polyester  styrene
 Disaccharides  Polyethylene  Synthetic polymer
 Ethylene  Polymer  terepththaleic acid
 Formaldehyde  Polymerization  Tetraf luoroethylene
 Homopolymer  Polymethyl  Thermoplastic
 Isoprene methacrylate (PMMA  thermosetting
 Methyl methacrylate  Polypropylene  Vinyl chloride
 Monomer  Polystyrene
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CHEMISTRY GRADE 12
Part I: Multiple Choice Questions
1. Which of the following statement is incorrect about polymers?

A. they are macromolecules made from smaller units.
B. they can be prepared by either condensation or addition polymerization.
C. most condensation polymers are hompolymers.
D. disposing synthetic polymers can pollute the environment.
2. The process by which monomer units combine to form polymers, is:
A. condensation C. thermoplastic
B. thermosetting D. evaporation
3. What is the molar mass of a polyethylene sample, [— CH2 —CH2—]n , when n =
4600? (Atomic mass, H = 1 and C = 12).
A. 1.288 ×103 g/mol C. 1.196 × 103 g/mol
B. 1.288 × 105 g/mol D. 1.196 × 104 g/mol
4. Which one of the following is not formed by addition polymerization? a polyethylene
c teflon b polyvinyl chloride d Dacron
5. Which one of the following polymer-monomer pairs is incorrectly matched?
A. Teflon-propylene
B. PVC-chloroethene
C. Plexiglass-methyl methacrylate
D. Bakelite-phenol and formaldehyde
6. Which one of the following is not a synthetic polymer?
A. nylon C. teflon
B. cotton D. dacron
7. Polyethylene is not used for making:
A. squeeze bottles C. electrical insulation
B. trash bags D. airplane windows
8. Dacron is made by the polymerization of ___________ and ______________.
A. terephthalic acid, ethylene
B. adipic acid, ethylene glycol
C. terephthalic acid, ethylene glycol
D. adipic acid, hexamethylene diamine
9. Which one of the following is a thermosetting plastic?
A. polyethylene C. dacron
B. polypropylene D. bakelite
10. Which of the following structures represents the monomer of -[-CH2 -CH2 =CH-
CH2-]-n ?
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POLYMER
A. CH3CH=CHCH3 C. CH2=CH—CH2—CH3
B. CH2=CH—CH=CH2 D. none of the above
11. (19)A disaccharide made from two glucose units that are linked by α-1,4 glycosidic
bond is:
A. cellulose C. lactose
B. maltose D. sucrose
12. (20) Which one of the following disaccharides is prepared from two different mono-
saccharide units?
A. Cellulose C. Lactose
B. Maltose D. Fructos
1. Define each of the following terms and give an example for each:
A. Monomer C. Carbohydrate
B. Polymer D. Amino acid
2. Classify each of the following polymers as natural or synthetic.
A. Polyethylene F. Polytetrafluoroethylene
B. Polypropylene G. Polystyrene
C. Cellulose H. Nylons
D. Dacron I. Cotton
E. Deoxyribonucleic acid J. Polyvinyl chloride
3. Classify each polymer in Question 2 as an addition polymer or a condensation poly-
mer.
4. What functional groups are involved in the addition and condensation polymerization
processes?
5. Mention major uses of each of the following synthetic polymers.
A. Polypropylene D. Polystyrene
B. Polyvinyl chloride E. Bakelite
C. Teflon F. Nylon
6. Why are olefins (alkenes) good monomers for polymerization reactions?
7. How does the molecular-level structure of these polymers influence their physical
properties?
8. Besides the extent of branching, can you think of any other structural parameters that
might lead to the differences in physical properties?
9. What kind of structural changes accompany bond-breaking and bond-forming in
olefin polymerization?
10. Draw the structure of the copolymer of:
A. HO–CH2CH2–OH and HOOC–CH2CH2–COOH.
11. What is the role of a catalyst?
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CHEMISTRY GRADE 12
12. Does ethylene polymerize under mild conditions in the absence of a catalyst (initia-
tor)?
13. Teflon” is the polymer that results from the polymerization of tetrafluoroethylene.
Write a chemical formula for this reaction. What are some of the properties of Teflon?
14. A polymer’s structure influences its physical properties. Describe two structural varia-
tions that are possible for polypropylene but not for polyethylene.
15. Consider the polymerization of vinylidene chloride, CH2=CCl2. What structural varia-
tions are possible in poly (vinylidene chloride)?
16. Consider the polymerization of 1,2-dichloroethylene, H(Cl)C=C(Cl)H. What struc-
tural variations are possible in poly(1,2-dichloroethylene)
204
Introduction to Environmental Chemistry
UNIT 5
INTRODUCTION TO
ENVIRONMENTAL CHEMISTRY
Unit outcomes
At the end of this unit, students will be able to

 define environmental chemistry
 describe the components that make the Environment
 explain environmental pollution
 identify the three types of environmental pollution and names of the
pollutants
 discuss the causes and effects of air, water and land pollution
 describe the main methods to reduce air, water and land pollution
 discuss air, water and soil pollution
 describe pollutants of the environment
 List greenhouse gases and describe their effect
 discuss about global warming and climate change
 apply pollution control mechanisms for controlling environmental
pollution
 describe about principle of green chemistry and cleaner production
 Apply the principle of green chemistry and cleaner production in doing
experiments
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CHEMISTRY GRADE 12
Startup Activit
When we see the word “Environmental Chemistry”, several meanings and
questions come into our mind.
• What do we understand the term Environmental Chemistry?
• Why is it important to know about Environmental Chemistry?
• What areas of knowledge are related to Environmental Chemistry, and
how can we use this knowledge?
5.1 Introduction
At the end of this subsection, you will be able to

 define environmental chemistry
 define terms related to environmental chemistry
 list the components of the environment
 describe the components of the environment
 write the important reaction in each component of the environment and
explain it how it happens in the environment
 describe the cycle of hydrological, Carbon, Nitrogen, Oxygen, sulfur
and phosphorus and explain how it is occurred in the environment
Activity 5.1
Discuss the following questions in groups and present your opinion to the class.
1. Why environmental chemistry is seen as a multidisciplinary?
2. Take CO2 as an example of a typical pollutant, and describe its
interaction with ecosystem and eventually its fate in the environment.
Environmental chemistry is a branch of chemical science that deals with the production,
transport, reactions, effects, and fates of chemical species in the water, air, terrestrial, and
biological environment and the effects of human activities thereon.
A common pollutant species is used to illustrate the definition of environmental chemistry.
Sulfur in coal is oxidized to sulfur dioxide gas, which is then released into the atmosphere.
Sulfur dioxide gas can be oxidized to sulfur trioxide and eventually converted to sulfuric
acid in the atmospheric, then fall back to earth as acid rain, affect a receptor like plants,
and end up in a “sink” like a body of water or soil. Figure 5.1 shows a simplified schematic
diagram that shown some of the interaction that occurred in the environment.
206
Figure 5.1: Simplified schematic diagram of definition of environmental Chemistry
5.1.1 Components of the Environment
Activity 5.2
Discuss the following questions in groups and present your answer to the class.
5. What portion of the environment’s component is included in the
hydrosphere?
6. The biosphere component of the environment refers to?
The environment consists of various compartments, including

• Atmosphere
• Hydrosphere
• Lithosphere
• Biosphere
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CHEMISTRY GRADE 12
Figure 5.2: Components of the environment (atmosphere, hydrosphere, lithosphere &

Biosphere)
The Atmosphere
One of the main components of Earth’s interdependent physical systems is the atmosphere.
An atmosphere is the layers of gases surrounding a planet or other celestial body. Earth’s
atmosphere is composed of about 78% nitrogen, 21% oxygen, and one percent other gases.
In general, the following roles are played by atmosphere components in the environment:
• the atmosphere component of the environment protective blanket of gas
surrounding the earth (0 – 50 km)
• absorbs infrared (IR) radiation emitted by the sun and re-emitted from the
earth
• controls temperature of the earth
• allows transmission of significant amounts of radiation from near UV (300
nm) to near IR (2500 nm)
• blocks transmission of damaging UV radiation
For example, the following important reactions occurred in the atmosphere:
I. Nitric oxide is oxidized by oxygen to nitrogen dioxide in the presence of
ultraviolet light.
2 NO ( g ) + O2 ( g ) 
ultraviolet
→ 2 NO2 ( g )
SO2, SO3 and NO2 react with rainwater and form sulphurous acid (H2SO3), sulphuric
acid (H2SO4 ) and nitric acid (HNO3 ), respectively and cause acid rain.
II. Chlorofluorocarbons are used as refrigerants, solvents and plastic foam-blowing
208
agents. When entering the atmosphere, they penetrate into the upper layers and
interact with ultraviolet radiation as follows.
CFüCl + UV 
yields
→ CF Cl ' + Cl '
The free chlorine Cl reacts with ozone to form chlorine monoxide and oxygen.
Cl ü + O3 Yields
 → ClO + O2
The Hydrosphere
“The hydrosphere is the combined mass of water found on, under, and above the surface of
the earth”. The hydrosphere includes water that is on the surface of the planet, underground,
and in the air. And it is collective term for all different forms of water, including oceans,
seas, rivers, lakes, streams, reservoirs, glaciers, and ground waters. Only ~1% of global
water supply is fresh water. Whereas, the greatest source of water on the planet is the
ocean, which constitutes all salt water and at the same time, is the greatest source of water
vapor. In the ocean, there are at least 77 important elements such as sodium and chlorine,
magnesium and bromine, which are commercially exploited from seawater.
Some examples of chemical reaction in hydrosphere:
I. Ammonia (NH3)/Ammonium (NH4+) that discharged from agriculture,

aquaculture, industry and urban area into large water bodies result in toxicity to
fish or aquatic ecosystem.
 For example, the biological oxidation of NH4+ to nitrite and then nitrate is a
key part of the complex nitrogen cycle and a fundamental process in aquatic
environments, having a profound influence on ecosystem stability and
functionality.
Nitrate (NO3-)/Nitrite (NO2-) that discharged from agriculture, industry,
aquaculture and sewage into water bodies result in accelerating aquatic plant
growth leading to eutrophication.
 For example, the organic form of nitrogen, ammonia, has been converted into an
inorganic form of nitrogen, nitrate that plants can use. The chemical equation:
2 NH 3 + 3O2 → 2 NO2 − + 2 H + + 2 H 2O
The equation summarizes the entire nitrification process.
The Lithosphere
The lithosphere consists of earth’s crust and upper mantle in which the crust part is the
Earth’s outer skin that is accessible to humans being. This part of the earth i.e. the crust
consists of rocks and soil (most important part to humans and the environment). Some
examples of important reaction in lithosphere are:
I. Different bacteria (mainly autotrophic, i.e., not dependent on organic material for
209
CHEMISTRY GRADE 12
their carbon supply) can effect oxidation or reductions of minerals.
1
2 FeCO3 + O2 + 3H 2O →Ferrobacilha
2 Fe ( OH )3 + 2CO2
2
II. Chemical weathering of rocks:
Fe2O3 + 3H 2O 
Yields
→ Fe2O3 3H 2O (Hydration of rocks)
The Biosphere
It refers to the realm of living organisms and their interactions with the environment (i.e.,
other compartments). This compartment divided into smaller units called ecosystems. Each
ecosystem contains dynamic interrelationships between living forms and their physical
environment. These interrelations manifest as natural cycles, such as hydrologic, oxygen,
nitrogen, phosphorous and sulfur. The natural cycles operate in a balanced manner providing
a continuous circulation of essential constituents. Examples of some important reaction in
the biosphere:
I. Photosynthesis:
6CO2 + 6 H 2O →
Sunlight
C6 H12O6 + 6O2
II. Respiration:
C6 H12O6 + 6O2 

Yields
→ 6CO2 + 6 H 2O + Heat energy
5.1.2 Natural Cycles in the Environment
Activity 5.3
Discuss the following in your groups and present into the class
1. In the oxygen cycle, what is the role of photosynthesis from the
environment perspective?
2. What is the Nitrogen Cycle and why is it Key to Life?
Within the environment, natural cycles serve to continuously circulate constituents essential
to life and other processes on earth.
• Hydrologic cycle
• Oxygen cycle
• Nitrogen cycle
• Phosphorous cycle
• Sulfur cycle
• Carbon cycle
210
The Hydrologic Cycle

Hydrologic cycle is arguably the most important natural cycle. In this cycle there is the
continuous exchange of water between environmental compartments. 10% of evaporative
losses from oceans precipitate on land (groundwater). Groundwater percolates by capillary
action to surface soil.
Figure 5.3: The hydrological cycle (water cycle)
The Oxygen Cycle

The oxygen cycle is the important cycle in the environment. Important to atmospheric
chemistry, geochemical transformation and life processes. The following reactions show
the importance of the oxygen cycle in the environment. For:
 Energy production
CH 4 + 2O2 
Yields
→ CO 2 + 2 H 2 O + Heat energy
 Degradation of organic material
CH 2O + O2 Yields
 → CO 2 + H 2 O
 Weathering of minerals
4 FeO + O2 
Yields
→ 2 FeO3
 Photosynthesis
CO2 + H 2O 
Yields
→ CH 2O + O 2
 Sun screen (O3)
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CHEMISTRY GRADE 12
' O′ + O2 
Yields
→ O3
Figure 5.4: The oxygen cycle
The Nitrogen Cycle

The nitrogen cycle is arguably the second most important cycle, after the carbon cycle,
to living organisms. Nitrogen is essential to plant growth, and therefore is a significant
contributor to the human food chain, but its presence in the environment is strongly
influenced by anthropogenic activities. The following are the important reaction of nitrogen
cycle in the environment:
 Fixation by bacteria and algae :
2 N 2 + 3CH 2O + 3H 2O + 4 H + 
yields
→ 3CO2 + 4 NH 4+
 Nitrification by nitrosomas and nitrobacteria :
2O2 + 3 NH 4+ 
Yields
→ NO3− + 2 H + + H 2O
 Nitrate reduction by microbial action :
2 NO3− + CH 2O 
Yields
→ 2 NO2− + H 2O + CO2
2 NO2− + 3(CH 2O) + 4 H + Yields

 → 2 NH 4+ + H 2O + 3CO2
 Denitrification returns N to the atmosphere:
2 NO3− + 5(CH 2O) + 4 H + 

Yields
→ 2 N 2 + 7 H 2O + 5CO2
 Perturbed by anthropogenic activity:
N 2 + O2 +… 
Yields
→ ( combustion ) NOX +…
212
Figure 5.5: The Nitrogen cycle
The Phosphorous cycle
The phosphorus cycle is responsible for increasing the availability of phosphorus in the soil
for plant growth and soil fertility. Understanding the mechanism of the phosphorus cycle
helps to understand the physiology of different microorganisms involved in the process.
• Central to many processes, including

• Cell division involving production of DNA and RNA
• Growth/maintenance of animal bones and teeth
• Sources include
• Inorganic phosphorous, such as soluble H2PO4-, HPO4- and insoluble
Ca5(OH)(PO4)3 and Fe3(PO4 )2•8H2O
• Terrestrial plants convert inorganic phosphate salts to organic phosphate
• Animals obtain phosphate by eating plants
• Upon death, phosphorus is returned to soil
• Soil microorganisms convert returned phosphate into soluble inorganic
phosphate (mineralization)
• In water, P solubility is controlled by availability of Fe and Al (under acidic
conditions) and Ca (under basic conditions
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CHEMISTRY GRADE 12
Figure 5.6 The phosphorus Cycle
The Sulphur Cycle
The sulphur cycle is essential as it balances the concentration of sulfur in different reservoirs
so as to make the Earth a hospitable place for life. Sulfur cycle show the circulation
of sulfur in various forms through nature. Sulfur occurs in all living matter as a component
of certain amino acids. It is abundant in the soil in proteins and, through a series of microbial
transformations, ends up as sulfates usable by plants. The following are importance of
sulfur cycle in the environment.
• Atmospheric oxidation produces higher charge states

• In hydrosphere and soil, S is present in many inorganic and organic forms with
oxidation states from -2 to +6
• Most common forms of S include
• Sulfate (SO42- ), produced via a variety of pathways (e.g., bacterial):
2 H 2 S + 4O2 → 4 H + + 2 SO4 2−
• Sulfide (S2- ), produced by reduction of sulfate in organic rich reducing
aqueous environments:
SO4 2− + 2CH 2O + H + → H 2 S + 2 H 2O + 2CO2
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5.1.3 Concepts Related to Environmental Chemistry
Activity 5.4
Discuss the relationship between concepts like pollutant, contaminate, BOD,
COD, sink and Threshold Limit Value with Environmental pollution and
present your answer to the class?
Pollutant: -A substance whose concentration has increased due to human activity,

ultimately having detrimental effects on the environment. Examples include sulfur dioxide
(SO2), carbon dioxide (CO2), ozone (O3), Pb, Hg, excess heat, light and sound.
Contaminant: - A substance that does not occur in nature, but it is introduced into the
environment through human activity. A contaminant is called a pollutant when it exerts
detrimental effects on human health receptor. Examples include bodies of water, humans,
trees, animals and fish.
Sink: - The medium that interacts and retains pollutants or converts them chemically
Dissolved Oxygen (DO): - Oxygen dissolved in water. It is vital for aquatic life. The
optimum levels of DO in good quality water are 4 – 8 mg L-1. Whereas water with levels
< 4 mg L-1 is considered polluted and unfit for human or animal consumption.
Chemical Oxygen Demand (COD): - An index of the organic content of water. Most
common sink of DO is oxidation of dissolved organic matter (DOM). COD of a water
sample is determined by chemical oxidation of the DOM by K2Cr2O7 in 50% H2SO4.
Other oxidizable species also react with dichromate, so typically gives erroneously high
measurements of DOM.
Biological Oxygen Demand (BOD): - Indicates the capacity of the DOM in a sample of
water to consume oxygen. Determined experimentally by measuring DO at beginning and
end of a 5-day period in a sealed sample. It also gives the measure of oxygen utilized as a
result of oxidation of DOM present in the water sample.
Threshold Limit Value (TLV): - Indicates the permissible level of a toxic pollutant in the
atmosphere to which a healthy individual can be exposed during an 8-hour day without
adverse effects. TLV is found by experimentation on animals, medical knowledge and
environmental studies
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CHEMISTRY GRADE 12
Exercise 5.1
1. The hydrosphere components of the environment include what part of the
environment and give examples of it?
2. Chlorofluorocarbons are used as refrigerants, solvents and plastic foam-
blowing agents. Have a chance to enter in the atmosphere and penetrate
into the upper layers and interact with ultraviolet radiation. Please write a
chemical reaction equation which shows how the ClFCs deplete the ozone
layer.
3. In oxygen cycle the two important reactions are degradation of organic
material and photosynthesis could express these two important reactions in
terms of chemical equation.
4. Write the equation that express Nitrogen fixation by bacteria and algae?
5. Define what mean pollutant and give examples of pollutants.
6. What mean threshold Limit Value (TLV)?
7. Describe the hydrological cycle?
8. What mean BOD and how it is measured experimentally?
5.2 Environmental Pollution

 explain environmental pollution
 describe about air, water and soil pollution.
 describe pollutants of the environment
 list the names of common air, water and land pollutants;
 describe the effects of air pollutants;
 describe some of the main methods used to reduce air pollution;
 list some of the factors involved in water pollution and explain their
effects;
 describe some of the methods used to reduce water pollution;
 list some of the factors involved in land pollution and describe their
effects;
 describe some of the main methods used to reduce land pollution; and
 carry out a project on the effects(s) of an industry on environment
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Activity 5.5
Discuss the following questions in groups and present your opinion to the class.
1. Ethiopia’s 2015 Climate Commitment Sets a High Bar for National Climate
Action. What was this climate commitment to be intended taken by Ethiopia?
2. The Copenhagen summit was a popular international climate change summit.
What was the role played by Ethiopia? What were the major issues of the
summit?
3. Mention any activity in your area to bring awareness of air pollution and
global warming. Discuss in your group and present to the class.
Pollution is any discharge of a solid, liquid or gaseous substance or radiation (energy) into an
environment that causes unwanted changes. Pollution causes short-term or long-term harm
that affects the earth’s ecological balance and lowers the quality of life in the environment.
A pollutant is any substance that changes air, water or any other natural resource in a way
that impairs the use of the resource. Pollutants are discharged into the environment as a
result of natural events (like a volcanic eruption) and as a result of human activities (such
as the operation of chemical industries, agriculture, etc.). Pollutants can be classified by the
type of pollution they cause: air pollution, water pollution, and land pollution.
5.2.1 Air Pollution
Activity 5.6
1. Based on the situation of your locality, discuss the following issues in
groups and present the findings to the class:
a. List some human activities which contribute to air pollution.
b. How these activities contribute to air pollution?
c. What solutions do you recommend to overcome these problems?
d. What could be your contribution to reduce air pollutions?
2. Give your suggestions on the statement, ‘Air pollution anywhere is a
potential threat elsewhere.’
Air pollution is caused by the presence of contaminant gaseous substances in the air that affect
the lives of plants and animals on earth. Some common air pollutants are sulphur dioxide,
nitrogen oxides, carbon monoxide, ozone, hydrocarbons, particulates, chlorofluorocarbons
(CFCs), and lead compounds.
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CHEMISTRY GRADE 12
Sulphur dioxide (SO2): - This enters the atmospheric air from the combustion of coal and
petroleum, and during extraction of metals from their sulphide ores. It causes coughing,
chest pains and shortness of breath. It is thought to be a cause for bronchitis and lung
diseases. It slowly oxidizes to SO3 by reacting with the oxygen in the air.
Oxides of nitrogen: - These can be formed in the atmosphere by natural processes like
thunderstorms. Combustion of fossil fuel containing nitrogen compounds as impurities and
exhaust gases from furnaces and engines increase the amount of nitric oxide, NO, and
nitrogen dioxide, NO2, in the atmosphere. Nitric oxide, NO, catalyzes the decomposition
of ozone in the upper layer of the atmosphere to oxygen, thus decreasing the ozone layer:
2O3 ( g ) + NO 
Yields
→ 3O2 ( g )
Nitric oxide is oxidized by oxygen to nitrogen dioxide in the presence of ultraviolet light:
2 NO ( g ) + O2 ( g ) 
Yields
→ 2 NO2 ( g )
SO2, SO3 and NO2 react with rainwater and form sulphurous acid (H2SO3), sulphuric acid
(H2SO4) and nitric acid (HNO3), respectively and cause acid rain. Acid rain accelerates
corrosion and the deterioration of metals, buildings, statues and also causes tree defoliation,
release of heavy metal ions from soil into water courses and drop in the pH of water in
rivers and lakes.
Hydrocarbons and ozone are responsible for photochemical smog. It is characterized by a

reddish-brown haze containing substances irritating to the eye, nose, and lungs, and causes
extensive damage to vegetation. Considerable amounts of hydrocarbons are released into
the atmosphere by the evaporation of gasoline as un burnt hydrocarbons in auto exhaust.
These substances react with ozone to give compounds that contribute to the oxidizing
nature of photochemical smog.
Carbon monoxide: - Most of the carbon monoxide escapes into the atmosphere due to the
incomplete combustion of fuel. Prolonged exposure to carbon monoxide impairs vision,
produces headaches, and exerts strain on the heart. It also reduces the oxygen-carrying
capacity of the blood by reacting with hemoglobin.
Particulates: - Dust storms, forest fires, volcanic eruptions and human activities such as
mining and burning coal and oil increase the amount of solid particles in the air. Industrial
areas contain particles of limestone, fertilizers, coal, stones, cement and silica. These
particulates irritate the lungs and deleteriously affect breathing.
Chlorofluorocarbons (CFCs): - Chlorofluorocarbons are used as refrigerants, solvents

and plastic foam-blowing agents. When entering the atmosphere, they penetrate into the
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upper layers and interact with ultraviolet radiation as follows:
CF2Cl2 
UV
→ CF2Cl +Cl 
The free chlorine, Cl, reacts with ozone to form chlorine monoxide and oxygen:
Cl  + O3 → ClO + O2
These reactions result in the conversion of ozone to molecular oxygen and contribute to
depletion of the ozone layer. This situation in the upper atmosphere allows dangerous
ultraviolet radiation to reach the earth’s surface. This radiation causes skin cancer in human
beings.
Excess carbon dioxide: - The combustion of coal and petroleum to generate electricity,
move our vehicles, heat our homes and supply power to our industrial machinery causes a
significant increase in the concentration of carbon dioxide in the atmosphere. Combustion of
these fuels releases about 20 billion tonnes of CO2 annually. The increase in the concentration
of CO2 in the atmosphere has resulted in a rise in the average global temperature, owing
to the greenhouse effect. Carbon dioxide and water vapour absorb infrared radiation, re-
radiated from the earth, behaving like the glass in a greenhouse. Since CO2 and water
vapor absorb heat, they are called green-house gases. Due to the absorption of heat by the
greenhouse gases in the atmosphere, the overall effect is global warming (an increase in the
average temperature of our planet). This rise in global temperature causes melting of polar
ice and thus additional water flowing into the oceans. This situation, in turn, results in the
rising of the levels of seas and oceans, flooding of coastlines and lowland areas, which can
submerge these areas.
Heavy metals: Lead contamination in the atmosphere is a result of vehicle engines that use
fuels containing tetraethyl lead which is added to the fuel to reduce engine knocking. The
use of lead paints also contributes towards lead contamination. High levels of lead cause
damage to the brain, kidneys and liver.
What are the potential air pollutants in and around your home?
Methods of Reducing Air Pollution
Activity 5.7
Discuss in groups and present your ideas to the class.
1. Name the major air pollutants.
2. What methods do you recommend to reduce air pollution other than the
methods listed below?
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CHEMISTRY GRADE 12
The following are some of the ways to reduce air pollution:

• Using public transports
• Turn off the lights when not in use
• Recycle and Reuse
• No to plastic bags
• Reduction of forest fires and smoking
• Use of fans instead of Air Conditioner
• Use filters for chimneys
• Implement Afforestation
• Avoid using of products with chemicals
• Avoid usage of crackers
5.2.2 Water Pollution
Activity 5.8
1. In your community,
a. What are the major sources of drinking water?
b. What are the principal sources of contamination of surface water and
ground water?
c. What could be done to reduce these problems?
Discuss in groups and present your answer to the class .
Water pollution is the degradation of the quality of water brought by the discharge of
untreated sewage, industrial and agricultural waste, and oil spillage. In general, water is
said to be polluted if it contains matter that affects the health of living things or causes
damage to property. The major water pollutants are nitrate and phosphate fertilizers washed
out of the soil, phosphate detergents, untreated sewage, insecticides and herbicides, and the
heavy metal ion, acidic and/or basic residues released by industrial processes. Phosphate
and nitrate fertilizers washed out of the soil and phosphate detergents from untreated water,
enter natural water systems, such as streams, rivers, lakes, and seas. These dissolved minerals
are valuable nutrients for plants, and their discharge into the water systems accelerates the
growth of surface-water plants, such as algae. As a result, less light reaches the bottom-
living plants, which reduces the photosynthesis they need to live, and they die. When these
aquatic plants die, they rot under the action of bacteria which multiply greatly and consume
the oxygen dissolved in the water at a rate faster than natural aeration or photosynthesis
can replenish. Thus, the amount of oxygen in the water decreases. This depletion of oxygen
kills aquatic animals like fish. This sequence of events is called eutrophication.
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Insecticides (pesticides) and herbicides applied in agriculture may also be washed into
lakes, rivers, streams and seas. Some of the insecticides and herbicides do not decompose
easily and are persistent in the environment. Residues of these insecticides and herbicides
may enter the food chains and accumulate in an organism that is consumed by the next
organism. The increasing amount of insecticide and herbicide residue in the bodies of
animals causes health and behavioral problems. The release of heavy metal ions, acidic
and/or basic residues from industrial processes into natural water systems, such as lakes
and rivers, causes pH changes in the water. Water organisms need specific ranges of
water pH to survive, so these changes in pH can kill them. In the same way, increasing
concentrations of toxic metal ions kills some aquatic organisms. The release of untreated
sewage to natural water systems can spread water-borne diseases such as cholera, typhoid,
hepatitis, and polio.
Methods of Reducing Water Pollution
• Treatment of water before discharge into rivers and lakes.

• To avoid unnatural temperature changes in natural water systems, industries should
not discharge heat-ladened water into them.
• Recycling industrial and agricultural wastes.
• Using moderate amounts of agricultural chemicals and increasing the use of
organic fertilizers and biological methods to control pests.
5.2.3 Land Pollution
Activity 5.9
Discuss the following issues and present your answer to your class.
1. Have you observed any pollution of land in your environment and what are
the causes of land pollution?
2. Do you observe soil erosion in your area? What are the three major things
do you believe elected officials should take to decrease soil erosion in the
region you live?
3. What should be your responsibility in solving the land pollution problems
Land pollution is caused by things we put into it. It results from the spillage of oil, leaching
of harmful chemicals and heavy metal ions, and dumping of non-biodegradable wastes
such as plastics.
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CHEMISTRY GRADE 12
Causes of Land pollution
• Spillages of oil from leaking pipelines.

• Harmful heavy metal ions from buried waste leaching into water systems.
• Leaching of harmful chemicals from corroded metal drums which have been
buried underground.
• Dumping of non-biodegradable (do not decompose by the action of bacteria)
wastes like plastics which remain unchanged in the soil for decades or hundreds of
years. Their accumulation in the soil hinders air and water movement and affects
the growth of plants.
• Excessive use of synthetic fertilizers in agricultural activities also contributes
towards land pollution.
What are the contributions of commercial inorganic fertilizers to land pollution?

Methods of Reducing Land Pollution
Activity 5.10
What methods should be practiced in Ethiopian context to reduce land
pollution? Discuss in groups and present your opinion to the class.
Actions to be taken or methods to reduce land pollution:
• Make people aware of the concept of Reduce, Recycle and Reuse.

• Reusing materials help to reduce the requirement of harvesting resources.
• Reduce the use of pesticides and fertilizers in agricultural activities.
• Reduce the use of non-biodegradable materials
• Avoid buying packaged items as they will lead to creating garbage and end up in
the landfill site
• Ensure that you do not litter on the ground and do proper disposal of garbage.
• Buy biodegradable products
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5.2.4 Pollutants of the Environment
Activity 5.11
1. How acid rain is formed. Write the reaction that shows formation of acid rain
2. Are pollutants of land can cause air pollution and water pollution? Take one
example and show its interdependence?
What are the potential pollutants of the environment while you are discussing air, water
and land/soil pollution? Environmental pollutants are chemicals that have ended up in the
environment as a result of human activities and that are hazardous to health. The common
Environmental pollutants of the environment are:
Lead: - This is a dangerous toxin found across the world, in fact, in all states. The element
readily dissolves in water and upon uptake leads to devastating health problems.
Methane: - This is a major component of natural gas, the gaseous form of fossil fuel. In
itself, it is harmless to the environment. However, it is one of the greenhouse gases
Plastic: - This is one of the most common environmental pollutants and bears one of the
greatest impacts. The abundance of plastics in the world even led to the coining of the term
“plastic pollution.”
Mercury: - This element is released into the environment due to mining activities, poor
disposal of certain items that are either made of mercury or had mercury in them. Batteries
are the main source of mercury, which is why it is essential to dispose of them carefully.
Fertilizers: - causes water pollution from excessive amounts of nitrates and phosphate
washed out from food and animal waste as well as inorganic fertilizers.
Volatile Organic Compounds (VOCs): - These are compounds that can easily become
gas or vapor. They are mostly released from the burning of gasoline, wood, natural gas,
and coal. Other sources of VOCs include thinners and paints, cigarettes, solvents, wood
preservatives, air fresheners, furnishings, copy machines and printers, cleaners, pesticides,
and disinfectants.
PCBs (polychlorinated biphenyl): - These are organic chlorine compounds that were at
one point extensively used as coolant fluids and dielectric in electrical gadgets, in heat
transfer fluids, and carbonless copy paper.
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CHEMISTRY GRADE 12
PROJECT 5.1
Develop a waste water treatment plan for your school and submit it to your teacher.
Exercise 5.2
1. Describe the main agents of:
a. air pollution b. water pollution c. land pollution
2. What are the impacts/effects of?
3. What are the main methods of reducing?
5.3 Global Warming and Climate Change

 describe global warming and climate change from the perspective of
chemistry
 list the common greenhouse gases
 describe greenhouse gases and greenhouse effect
 discuss about the chemistry of greenhouse gases related to global
warming
 Classify greenhouse gases
In this sub section, we will discuss the role of several chemical reaction that occur in the
atmosphere, as well as direct emissions of some greenhouse gases into the atmosphere
which cause to global warming. In general, the relationship between chemistry and climate
change will be explored under two headings: global warming and climate change from the
standpoint of chemistry, and greenhouse gas chemistry and its impacts on climate change.
5.3.1 Global Warming and Climate Change
Activity 5.12
Discuss in group and present your opinion to your class mates.
1. The role of industrially byproducts to global warming.
2. Types of activities which are happened in your surrounding that
contribute for global warming.
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Why chemistry is so important in the fight against climate change? Any human activity has
a definite impact on the environment. In this context, climate change is one of the main
current concerns and challenges for mankind. Data in our hands reveals the existence of a
global warming process and urgent actions are needed before dramatic and irreversible (on
a human scale) climate changes could take place. The emission of certain substances to the
atmosphere produces a greenhouse effect contributing to the global warming. Even if their
origin is diverse, many of these emitted gases or substances resulted from:
Certain type of chemical reaction mainly from combustion of fuel:
C X H Y + O2 
Yields
→ CO2 + heat energy
Where X and Y are carbon and hydrogen number of hydrocarbon compound.
• Some of them may be manufactured products like ClFCs, solvents and volatile or-
ganic compounds.
• Some of them have a natural origin, as it is the case of methane generated by living
organisms, in particular in the oceans.
• In other cases, however, they are associated with human activities. The most well-
known is carbon dioxide (CO2) and its increasing content in the atmosphere is main-
ly associated with the combustion of fossil fuels.
According to data from the US Department of Energy, global emissions of carbon

dioxide resulting from combustion of fossil fuels increased by larger than 10 factor since
1900. A variety of other gases contributes to the greenhouse effect, including solvents,
chlorofluorocarbons and other volatile organic compounds (VOCs), or nitrogen and sulphur
oxides. Some of them can have, intrinsically, an even greater greenhouse effect than CO2 but,
in general, are released to the atmosphere in amounts significantly lower. Besides, some of
them, like nitrogen oxides, are generated concomitantly to CO2 in combustion.
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CHEMISTRY GRADE 12
5.3.2 Chemistry of Greenhouses Gasses and their effects

on Climate change
Activity 5.13
Discuss the following questions in group and present your opinion to your class
mates.
1. Mechanism in which the greenhouse gases increase average earth’s temperature.
2. Composition and reactions of gases occurred in the atmosphere that contributes
for global warming?
Greenhouse Effect
The greenhouse effect happens when certain gases, which are known as greenhouse gases,
accumulate in Earth’s atmosphere. Greenhouse gases include carbon dioxide (CO2),
methane (CH4), nitrous oxide (N2O), ozone (O3), water vapor (H2O) and fluorinated gases.
These gases warm our planet by absorbing infrared (IR) light radiation that would otherwise
escape into space. Without this warming effect (called the greenhouse effect), the average
temperature on Earth would be a chilly 255 K (that’s -18 oC, or the temperature on an
extremely cold winter day). Because these greenhouse gases in our atmosphere absorb IR
light, Earth’s average temperature is 288 K (that’s 15 oC, about the temperature on a slightly
cool spring day). Thus, Earth is 33 K warmer than what would be expected if there was no
the greenhouse effect.
For example, CO2(g) and H2O(g) do absorb IR light and upon doing so gain energy which is
transferred to the rest of the Earth. Even though these gases are present in small amounts,
they are very good at absorbing infrared light. Thus, these atmospheric gases are the main
contributors to the greenhouse effect. On the other hand, both N2 (g) and O2 (g) are present in
very large amounts in the atmosphere, these gases do not absorb IR light and therefore do
not contribute to the greenhouse effect.
Composition of the atmosphere
Atmosphere is considered as solution. Several different gases make up our atmosphere

(Table 1). Because N2 (g) is a molecule present in greatest amount in the atmosphere, N2 is
the “solvent” in our atmospheric “solution”. The solute present in largest amount is O2 (g),
but certainly there are many others.
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Table 5.1 Gases Present in atmosphere

Name Percent by volume
Nitrogen 78%
Oxygen 21%
Argon 1%
Gaseous water 0 to 4 %
Carbon dioxide 0.04% and increasing
Contribution of Greenhouses Gases for Global warming
Do you know which greenhouse gases that human produce have the most impact on global
warming? Not all have the same effect, nor do they come from the same sources, and in
the same way each lasts for a different time in the atmosphere. Other variables such as
the formation of water of anthropogenic origin and black carbon in snow for their lesser
effect are excluded. There are five gases of human origin that contribute most – together up
to 95% of the total – to the increase in global warming. Here you will discover the source of
their emission, the time they spend in the atmosphere and what percentage they contribute
to the greenhouse effect in the following table.
Table 5.2: Sources, atmospheric life time and percentage of contribution of greenhouse
gases
Greenhouse gas The sources of their emission Time spent in atmo- %stage of
sphere contribution
to global
warming
Carbon dioxide Result of processes such as fuel 80% lasts for 200 52.92 %
use, deforestation and produc- years and the other
tion of cement and other mate- 20% can take up to
rials. 30,000 years to dis-
appear
Methane Generated by activities such as It lasts an average of 14.88 %
livestock production, agricul- 12 years in the atmo-
ture, sewage treatment, natural sphere
gas and oil distribution, coal
mining, fuel use and is also giv-
en off from waste tips
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CHEMISTRY GRADE 12
Halogenated com- Results from the production Depending on the 10.78 %

pounds (CFCs)& of chemicals by diverse sec- type of compound,
HCFCs tors such as refrigeration and their duration in the
air conditioning, electrical and atmosphere varies
electronic equipment, medi- from a few months to
cine, metallurgy, and so on tens of thousands of
years
Tropospheric ozone This is a product of the reaction These gases don’t 10.72 %
between the gases carbon mon- last as long in the at-
oxide (CO), nitrogen dioxide mosphere as others, a
(NO₂) and VOCs (Volatile Or- matter of months at
ganic Compounds), given off the most.
during the burning of fuels
nitrous oxide It comes mainly from the use Lasts longer in the 10.70 %
of fertilizers, fuel use, chemical atmosphere, up to
production and sewage treat- 114 years.
ment
Exercise 5.3
1. Write the general chemical reaction equation that express combustion of
fuel and result in increasing of global warming
2. List an example of greenhouse gases that contribute for Global warming
from anthropogenic and natural sources
3. Describe the composition of the atmosphere?
4. Describe the mechanism how greenhouse gases increase global warming?
5.4 Green Chemistry and Cleaner Production

 define the terms green chemistry and cleaner production
 discuss on the major principles of green chemistry and cleaner
production
 list the importance of cleaner production
 Explain atom economy
 Calculate the atom economy based on the given chemical reaction
 Apply green chemistry principles while doing laboratory activities
 Apply atom economy principle during designing chemical reactions
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Activity 5.14
Discuss the following issues in group and present your opinion to the class.
1. What can you do to “green” your day? How does this suggestion reduce
your ecological footprint?
2. Brainstorm the criteria for a “green” product.
What does it mean when you say “Green chemistry and cleaner production”? Have you
looked around?
Think about all of the different substances that you deal with on a daily basis. Consider your
notebook or the materials that help to deliver power to your calculator. How was the cover
of your notebook made? What will happen to it when you throw it away? What materials
were used to make the batteries or the solar cells in your calculator? What will happen to
these materials once they no longer work properly?
We are surrounded by a huge variety of materials with a wide range of chemical and
physical properties. We are continually developing processes to create products with desired
properties. Our ability to manufacture materials provides many conveniences, but also
some drawbacks. We are using raw materials at an alarming rate. We are also discarding
hazardous chemicals into our landfills or incinerating them and releasing chemicals into
our atmosphere.
We are starting to understand more about the hazards of chemical processes. Industries in
many countries are now paying attention to the fuels and raw materials they use and the by-
products they release along with their intended products. Sometimes manufacturers simplify
processes to fewer steps. This has many benefits, including reducing waste. Processes are
burning less fuel, using fewer toxic reactants, and releasing fewer unwanted by-products.
Industry is attempting to become “greener.”
In this sub section the principles of green chemistry and cleaner production will be discussed
in detail.
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CHEMISTRY GRADE 12
5.4.1 Principle of Green Chemistry
Activity 5.15
1. How green chemistry differs from cleaning up pollution?
2. Use of renewable feedstock is one of the principled of green chemistry,
and can be accomplished by increasing awareness of sustainability in our
modern society that led to switch to the use of biomass as a feedstock and
an energy source. What are other examples of renewable feedstock’s in
your surroundings?
“Green chemistry” is a movement to make industries that involve chemicals more

environmental friendly and sustainable. Green chemistry asks the question: “Why generate
pollution if there is a greener alternative?”
Developing a green alternative begins with considering the hazards of the required
chemicals as well as their properties. Chemists then develop a manufacturing process so
that every stage of product development is environmentally safe—from the raw materials
to what happens to the product at the end of its useful life. In other words, the process is
“benign by design.”
A green chemistry solution may involve using safer chemicals. Liquid carbon dioxide,
for example, is starting to replace toxic organic solvents used in dry cleaning. Greening
a chemical process can also involve making a process more efficient. For example, the
original makers of ibuprofen, an important pain reliever, found a way to make the drug
in half the number of steps. The result is a process that generates less waste, uses less
energy, and is more profitable! The “12” principle of green chemistry which are listed
below directly or indirectly involves both modern methods of pollution control mechanism
and cleaner production.
The “12” Principles of Green Chemistry

1. Prevention
The proper definition says that it is better to prevent waste than to treat or clean up waste after
it has been generated. Generally, it describes the ability to update chemical transformations
in order to limit the generation of hazardous waste as a significant advancement towards
contamination or pollution avoidance.
230
By preventing waste generation, the risks associated with waste storage, transportation,
and treatment could be limited. A solid example can be the pulp and paper industry, usage
of chlorine compounds in processes produce toxic chlorinated organic waste. Green
chemistry developed a method to convert wood pulp into paper using oxygen, water, and
polyoxometalate salts while producing only water and carbon dioxide as by-products. Isn’t
that great?
Simply, “Less Waste is directly proportional to Less Pollution”.
2. Atom Economy
The Atom economy is a primary criterion for green chemistry. The idea of the atom
economy is to improve chemical processes, by avoiding the waste of atoms from reactants
to products. Atom economy can be assessed easily by calculating the number of atoms in
the Chemical Reaction. Atom Economy is the ratio of “the mass of the desired product”
by “the total mass of the products”, and can be expressed in percentage as illustrated in the
formula below.
Assume for a reaction:
A + B → C + D, where ‘C’ is the desired product

The Atom Economy can be calculated as,
Atom economy ( Mass of C ) / ( Mass of C + D )  *100

=
For an optimal process, the atom economy should be near or equal to 100%.
Figure 5.7: simple diagrams which shows atom economic reaction
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CHEMISTRY GRADE 12
It is beneficial to promote the atom economy as it helps in:

• minimizes the waste, and reduces the cost associated with waste management and
treatment.
• simplifies storage and transportation.
• minimizes potential pollution
• prevents companies from legal pursuits and reduces emissions, etc.
3. Less Hazardous Chemical Synthesis

• Wherever practicable, synthetic methods should be designed to use or generate
chemicals that pose little or no toxicity to the environment and human health.
• The goal should be to avoid reactions that give hazardous by-products.
4. Design of safer chemicals
The design of safer chemicals deals with the rendering of chemicals which fulfill their
intended purpose and yet are benign and harmless to the ecosystems.
This modification should be reflected up to the molecular level of the chemical’s design.
5. Safer solvent and Auxiliaries
Most of the industries from polymer to pharmaceutical industries and other chemical allied
industries use solvents at some point in their manufacturing. In general, the use of solvents
should be avoided, but that is not possible in all cases. So we can possibly replace toxic,
non-recyclable solvents with safer and innocuous solvents.
6. Design for Energy Efficiency

Recognition of the energy requirements, their impact on the environment and economy,
and its minimization to the extent possible will pave way for a greener process. Processes
should be carried out at ambient conditions. Some ways in which this can be achieved are
well-maintained equipment in plants, recovery of waste heat, and removal of solvents,
proper utilization of catalysts, and combined heat and power (CHP).
7. Use of Renewable Feedstock
The increasing awareness of sustainability in our modern society has led to switch to the
use of biomass as a feedstock and an energy source.
8. Reduce Derivatives
In this principle, “the reaction takes place at a particular functional group blocking
unnecessary waste generation “by reducing the process steps with the use of enzymes,
catalysts, or solvent, therefore, reducing demand for feedstock and utilities required for
down-streaming hence increasing overall economy and efficiency of the process.
232
For example, the manufacturing of Ibuprofen (a painkiller) is a 6 step process by the

conventional methods. By using anhydrous HF the process minimizes to 3 steps which are
recyclable.
9. Catalysis
Catalysis is one of the most important pillars of Green Chemistry. “Stoichiometric”

technologies are the primary source of waste; on the other hand, “Catalytic Processes” are
achieving the goals of environmental protection and economic benefit.
Catalysts provide many benefits from lower energy consumption to increase selectivity of
the reaction and allow a decreased use of harmful and toxic chemical agents.
Zeolites, Clays are promising and benign catalysts used in Heterogeneous Catalysis, which
can replace the use of harmful catalysts. Enzymes are Biocatalysts which are natural
substances derived from biological sources, are renewable and Biodegradable.
Catalysis can help us build a more sustainable world and can play a major role to mitigate
the global environmental impacts of unsustainable chemical processes.
10. Design for degradation
This principle stands for, “Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do not persist in the
environment”. That means during the usage of chemicals it should be stable and do not
persist the environment but after usage, it should be degraded into small molecules that are
not harmful to the environment and humans.
Figure 5.8: Simple illustration of biodegradable product
233
CHEMISTRY GRADE 12
11. Real-time analysis for Pollution prevention
Just like watching the live news telecast i.e., in real-time makes it better to understand and
act best according to the situation. Real-time analysis in Chemical and allied industries are
essential for production, transportation, and especially in the case of pollution prevention.
Pollution in the industrial premises could become a potential threat to various probable
hazards. The real-time analysis opens the scope of online process control and prevents any
possible threats hence increasing overall profit to the industry as well as ensures safety to
the environment.
12. Inherently safer chemistry for accident prevention
It involves choosing a safe or safer chemical to mitigate the chances of occurrence of an

accident. It benefits the industry as well as the environment as it acts as a safeguard against
calamitous industrial or laboratory accidents. Avoidance of hazard is the key.
5.4.2 Cleaner production in chemistry
Activity 5.16
Consider any chemical reaction do think that one gram of reactants produces
one gram of a product/s? If not why? Discuss in groups and present your
opinion to the class.
An ideal chemical reaction should have a number of attributes such as
• safety
• simplicity
• selectively
• high yield
• energy efficiency
• use of renewable or recyclable raw materials and reagents
• absence of hazardous byproducts or at least minimizing or containing them
In practice, it is impossible to achieve all these attributes simultaneously. Indeed it is a

challenge for chemists and engineers to identify environmentally preferable reaction
pathways that optimize the balance of all the desirable attributes.
234
Goals of Green Chemistry
The goals of “green chemistry” perspective include the following:
 to reduce adverse environmental impacts by appropriate and innovative choice of

materials and their chemical transformation
 to develop processes based on renewable (plan-based) rather than non-renewable
(fossil carbon –derived) raw materials
 to develop products that are less toxic or which require less toxic raw materials/
feedstock’s
 To develop products that degrades more readily /rapidly in the environment than
the current products.
 to reduces the requirement for hazardous or environmentally persistent solvents
and extraction in chemical processes
 to improve energy efficiency by developing low temperature and low pressure
processes by using new/improved catalysts
 to minimize byproducts in chemical transformation through redesign of reactions
and reaction sequences. In other words, to achieve better” Atom economy”
 Formula weight of the product 

% of atom economy=   * 100
 sum of formula weights of all the reactants 
Good atom economy means most of the atoms of the reactants are incorporated in
the desired products and only small amounts of unwanted byproducts are formed
and hence lesser problems of waste disposal or waste treatment. It is better to see
atom economy in detail with illustrative example below:
Atom economy: The atom economy (a measure of atom utilization or efficiency) is a

measure of the amount of starting materials that end up as useful products. It is important
for sustainable development and for good economic reasons to use reactions with high
atom economy. A chemical reaction may give, and often does, more than one product, but
of the mixture of products, perhaps only one of them is the desired useful product. The
percentage atom economy of a reaction is readily calculated using the balanced equation
for the reaction expressed in reacting masses.
The atom economy of a reaction is a theoretical percentage measure of the amount of

starting materials that ends up as the ‘desired’ useful reaction products. It’s sometimes
referred to as atom utilization.
235
CHEMISTRY GRADE 12
Mass of desired or useful product

Atom economy = 100 *
Total mass of all reactants or products
In atom economy calculations you can say REACTANTS or PRODUCTS because of the
law of conservation of mass. The greater the % atom economy of a reaction, the more
‘efficient’ or ‘economic’ it is likely to be. Many reactions give more than one product, and
not all of them are useful, so it is useful to calculate what % of the products is theoretically
useful, and we call this the atom economy of the reaction. The reactions that only give
one product, have the maximum atom economy of 100% and these are the most economic
reactions e.g. synthesis of ammonia and reacting ethene with water to make ethanol.
N 2 + 3H 2 ⇒ 2 H 3 and CH 2 =
CH 2 + H 2 O ⇒ CH 3CH 2OH
Example of calculation of atom economy:
Fe2O3 ( s ) + 3CO ( g ) ⇒ 2 Fe ( l ) + 3CO2 ( g )
Using the atomic masses of Fe = 56, C = 12, O = 16, we can calculate the atom economy
for extracting iron based on the above reaction.
Solution:
[(2 x 56) + (3 x 16)] + [3 x (12 + 16)] ===> [2 x 56] + [3 x (12 + 16 + 16)]

[160 of Fe2O3] + [84 of CO] ===> [112 of Fe] + [132 of CO2]
so, there are a total of 112 mass units of the useful/desired product iron, Fe,
out of a total mass of reactants or products of 160 + 84 = 112 + 132 = 244.
Therefore, the atom economy = 100 x 112 / 244 = 45.9%
Note: It doesn’t matter whether you use the total mass of reactants or the total mass
products in the calculations; they are the same due to the law of conservation of mass. Why
the reaction with only one product will always give the highest atom economy?
236
Exercise 5.4
1. Give examples of a green chemistry solution that involve safer chemicals.
2. Explain what cleaner production means?
3. Which principle of green chemistry best explained in cleaner production?
4. Green chemistry aims to?
A. Design chemical products and process that maximize profits
B. Design safer chemical products and processes that reduce or eliminate
the use and generation of hazardous substances
C. Design chemical products and processes that work most efficiently
D. Utilize non-renewable energy
5. Which of the following is a challenge for green chemists?
A. Awareness of the benefits of green chemistry
B. Developing chemicals that are recyclable
C. Training for cleaning up chemical spills
D. Knowing when to reduce and eliminate hazardous waste
5. Environmental benefits of green chemistry include?
A. Fewer raw materials and natural resources used
B. Cleaner production technologies & reduced emissions
C. Smaller quantities of hazardous waste to be treated and disposed of
D. All of the above
6. Calculate the atom economy of the fermentation of sugar to make ethanol
(‘alcohol’)
237
CHEMISTRY GRADE 12
Unit Summary
~ Environmental chemistry encompasses a number of fields of chemistry and
chemical processes that take place in soil, water, air, and in living systems.
~ Environmental chemistry is the branch of chemical science that deals with the
production, transport, reactions, effects, and fates of chemical species in the water,
air, terrestrial, and biological environment and the effects of human activities
thereon.
~ The environment consists of various compartments, including: atmosphere,
hydrosphere, lithosphere and biosphere
~ Examples of some important reaction in the biosphere:
Photosynthesis: 6CO2 + 6 H 2O → C6 H12O6 + 6O2 and

sunlight
~
~ Respiration: C6 H12O6 + 6O2 

Yields
→ 6CO2 + 6 H 2O + Heat energy
~ Pollutant: A substance whose concentration has increased due to human activity,

ultimately having detrimental effects on the environment
~ Pollution is any discharge of a solid, liquid or gaseous substance or radiation
(energy) into an environment that causes unwanted changes.
~ Pollutants can be classified by the type of pollution they cause: air pollution, water
pollution, and land pollution.
~ Air pollution is caused by the presence of contaminant gaseous substances in the
air that affect the lives of plants and animals on earth
~ Some common air pollutants are sulphur dioxide, nitrogen oxides, carbon
monoxide, ozone, hydrocarbons, particulates, chlorofluorocarbons (CFCs), and
lead compounds.
~ Water pollution is the degradation of the quality of water brought about by the
discharge into it of untreated sewage, industrial and agricultural waste, and oil
spillage.
~ The major water pollutants are nitrate and phosphate fertilizers washed out of
the soil, phosphate detergents, untreated sewage, insecticides and herbicides, and
the heavy metal ion, acidic and/or basic residues released by industrial processes
~ Land pollution is caused by things we put into it. It results from the spillage of
oil, leaching of harmful chemicals and heavy metal ions, and dumping of non-
biodegradable wastes such as plastics.
~ The emission of certain substances to the atmosphere produces a greenhouse effect
contributing to the global warming. The greenhouse effect happens when certain
gases, which are known as greenhouse gases, accumulate in Earth’s atmosphere.
~ Greenhouse gases include carbon dioxide (CO2), methane (CH4), nitrous oxide
(N2O), ozone (O3), and fluorinated gases.
~ Because N2 (g) is the compound present in greatest amount in the atmosphere,
N2 is the “solvent” in our atmospheric “solution”. The solute present in largest
amount is O2 (g), but certainly there are many others.
238
~ “Green chemistry” is a movement to make industries that involve chemicals

more environmentally friendly and sustainable.
~ Developing a green alternative begins with considering the hazards of the
required chemicals as well as their properties
~ A green chemistry solution may involve using safer chemicals.
~ One of the principles of green chemistry, chemists should develop a
manufacturing process so that every stage of product development is
environmentally safe—from the raw materials to what happens to the product
at the end of its useful life.
 Formula weight of the product 

% of atom economy=   * 100
 sum of formula weights of all the reactants 
~ Good atom economy means most of the atoms of the reactants are
incorporated in the desired products and only small amounts of unwanted
byproducts are formed and hence lesser problems of waste disposal or waste
treatment)
Check List
Key terms of the Unit
 Agents of land  Climate Change  Green Chemistry
pollutant  Components of  Greenhouse effect
 Agents of water environment  Greenhouses Gasses
pollutant  Contaminate  Land Pollution
 Air pollutant  Environmental  Pollutant
 Air Pollution chemistry  Principle of Green
 Atom Economy  Environmental chemistry
 cleaner production Pollution  Safer solvent
 Climate Change  Global Warming  Sink
239
CHEMISTRY GRADE 12

Part I: True or False Item Questions
1. Green chemistry can provide green technology solutions for a sustainable future?
2. Bio-catalysis has become very useful in green chemistry manufacturing?
3. Green chemistry is more expensive than traditional chemistry?
4. Pollutant is a substance, whose concentration has increased due to natural activity.
5. It is better to prevent waste than to treat or clean up waste after it has been generated
is one of the important principles of green chemistry.
Part II: Multiple-Choice Questions

1. Green chemists reduce risk by?
A. Reducing the hazard inherent in a chemical product or process

B. Minimizing the use of all chemicals
C. Inventing technologies that will clean up toxic sites
D. Developing recycled products
2. The first listed of the 12 Principles of Green Chemistry is?
A. Prevent waste B. Catalysis C. Atom economy D. Benign solvents
3. Which of the following is the greenest solvent?
A. Formaldehyde B. Benzene C. Ethanol D. Water

4. ________ is an excellent ‘green’ solvent as well as a greenhouse gas?
A. Methanol B. CFCs C. Carbon monoxide D. Carbon Dioxide

5. Benzene, a _______ substance, is an important industrial solvent used in the
production of
pharmaceuticals, plastics, and dyes?

A. Odorless B. Non-flammable C. Biodegradable D. Carcinogenic
6. The gases that contribute to the greenhouse effect on Earth are, in order of greatest to
smallest in importance
A. CO2, H2O, CH4 B. H2O, CO2, CH4
C. CH4, CO2, H20 D. H2O, CH4, CO2
7. Which of the following is an example of impact of development activities on the
240
hydrosphere?
A. Air pollution B. Soil pollution C. Soil erosion D. Water pollution
8. What is the source of carbon monoxide?
A. incomplete burning of wood B. fuels
C. exhaust fumes of motor vehicles D. all of above
9. What is the source of sulfur dioxide?
A. PowerStation’s and industries using fossil fuels B. exhaust fumes of motor vehicles
C. incomplete burning of wood D. none of above
10. Which of the following will not cause any atmospheric pollution?
A. Hydrogen B. Sulphur Dioxide C. Carbon dioxide D. Carbon monoxide
11. Photochemical smog is related to the pollution
A. Soil B. Water C. Noise D. air
12. The largest reservoir of nitrogen in our planet is:
A. Ocean B. Atmosphere C. Biosphere D. Fossil fuels
13. Most important causative pollutant of the soil/land
A. plastics B. iron junks C. detergents D. glass junks
14. Depletion of ozone layer is due to oxide of
A. Carbon B. phosphorus C. nitrogen D. None
15. Greenhouse effect is caused
A. Those gases which absorb the infrared light reflecting from earth
B. CH4, SO2 and NO2 C. CO2 only D. None of the above
16. The result of ozone hole is
A. acid rain B. Global warming
C. the UV radiations the earth D. Greenhouse effect
17. Which of the following gases contribute to the global warming?
A. Carbon monoxide B. Sulphur dioxide
241
CHEMISTRY GRADE 12
C. carbon dioxide D. nitrogen dioxide
18. Which of the Following Greenhouse Gases Is Present in Very High Quantities?
A. Carbon dioxide B. Ethane C. Propane D. Methane
19. Burning of Fossil Fuels Results In
A. Increased oxygen level B. Decreases greenhouse gases
C. Increased greenhouse gases D. Increased ethane level
20. One of the following is Naturally Occurring Greenhouse Gas?
A. Nitrous oxide B. Methane C. Carbon dioxide D. Ethane
21. N 2 + O2 
Yields
→ 2 NO
2 NO + O2 
Yields
→ 2 NO2
NO2 Yields
 → NO + O
O + O2 
yields
→ O3
The above reactions describe the chemical process that forms:
A. Photochemical smog B. Industrial smog’ C. Acid precipitation D. Ozone
22. One of the following is not true about the role of catalyst in cleaner production?
A. allows a decreased use of harmful and toxic chemical agents
B. enzymes are Biocatalysts are not renewable and Biodegradable
C. increased selectivity of the reactions D. Lower energy consumption
Part III: Short Answer Questions

1. Why is it called the “greenhouse” effect?
2. Do all greenhouse gases have the same effect?
3. Carbon monoxide is more dangerous than carbon dioxide. Why?
4. List common water, air and soil pollutant?
5. Describe the mechanism to reduce, water, air and soil.
6. What is greenhouse effect? Which gas is mainly responsible for global warming?
7. What is atom economy? What implies that the reaction has good atom economy?
8. Write at least 5 Green chemistry principle most commonly practiced in your
surrounding?
242
Part IV. Problem

1. Write a brief note about “What does “Green chemistry and cleaner production mean?”
2. Write a brief note on adverse effects of specific metal pollutants.
3. Consider the following three reactions “A”, “B” and “C”

Reaction A: converting ethanol to ethene
Reaction B: ethene + water ===> ethanol
Reaction C: fermentation of sugar to make ethanol (‘alcohol’)
Calculate the atom economy of the above reaction A, B and C. Both reaction B
and C are gives the same desired product ethanol, which is more environmental
friendly? And give your reason?
243

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CHEMISTRY

UNIT 1: ACID-BASE EQUILIBRIA

1.1 ACID-BASE CONCEPTS ...........................................................3

1.5 Acid–Base Indicators and Titrations........................................38

UNIT 2: ELECTRO CHEMISTRY

2.1 OXIDATION-REDUCTION REACTIONS............................50

3.1 Introduction ...........................................................................120

4.1 Introduction to polymers........................................................ 184

UNIT 5: INTRODUCTION TO ENVIRONMENTAL

5.1 Introduction ...........................................................................206

5.3 Global Warming and Climate Change ..................................224

At the end of this unit, you will be able to:

1.1 ACID-BASE CONCEPTS

 calculate pH from  H +  and  H +  from pH calculate pOH from

OH −  and OH −  from pOH

1.1.1 Arrhenius concept of acids and bases

In Arrhenius’s theory, a strong acid is a substance that completely ionizes in aqueous

solution to give H 3O + (aq) and an anion. An example is perchloric acid, HClO4

b. NaCl ( s ) + H O(l ) → Na + (aq ) + Cl − (aq )

1.1.2 Brønsted-Lowry Concept of Acids and Bases

In this reaction water acts as an acid. It gives up a proton (H+) to NH 3 , a base. As a

produced by the ionization of the hypothetical NH 4OH of the Arrhenius theory.

1.1.2.1 Conjugate acid-base pairs

Conjugate acid - base pair

CH 3COOH (aq )+ H 2O(l )  CH 3COO − (aq ) + H 3O + (aq )

up by H 2O . Thus, H 2O acts as a base. In the reverse reaction, the hydronium ion, H 3O +

Table 1.1: The conjugate pairs in some Acid-Base Reactions.

Acid + Base ⇌ Base + Acid

HCl + H 2 PO4 −  Cl − + H 3 PO4

Strengths of Conjugate Acid-Base Pairs

How do you know the strengths of conjugate acid- base pairs?

Chart 1.1: Strengths of Conjugate Acid-Base Pairs.

1.1.2.2 Auto ionization of substances

Name the ions present in water. How are they formed?

2 H 2O(l )  H 3O + (aq ) + OH − (aq )

1.1.2.3 Amphiprotic Species

base NH 3 and with the acid CH 3COOH (acetic acid)

reacts as a base with the acid CH 3COOH .

1.1.3 Lewis concept of acids and bases

 A base is any species that donates an electron pair to form a bond.

as the B atom in BF3 , and

2. a species that has lone-pair electrons such as N in NH 3

CaO + CO2 → CaCO3

BeCl2 + 2Cl − → BeCl4 2−

1.2 IONIC EQUILIBRIA OF WEAK ACIDS AND BASES

 derive the expression of ion product for water, K w

 use K w to calculate  H 3O +  or OH −  in aqueous solution;

 write the expression for the acid-dissociation constant, K a ;

 calculate K a for an acid from the concentration of a given solution and

 calculate  H +  and pH of an acidic solution from given values of K a

 write the expression for the base-dissociation constant, K b ;

1.2.1 Ionization of water

How do you calculate the concentration of H 3O + ions if the concentrations of OH − ions

Although pure water is often considered a non-electrolyte (nonconductor of electricity),

H 2O(l ) + H 2O(l )  H 3O + (aq ) + OH − (aq )

Like any equilibrium process, the auto-ionization of water is described quantitatively by

remains essentially constant, about 56 Mat 25oC, we multiply Kc by [ H 2O ] to obtain a

new equilibrium constant, the ion-product constant for water, K w :

varies with temperature. At body temperature (37oC), K w equals 2.5 x 10-14.

Thus, the concentrations of H O + and OH − are both 1.0 x 10 -7 M in pure water.