NATURAL RESOURCES DEVELOPMENT COLLEGE

OPEN AND DISTANCE LEARNING UNIT

(DEPARTMENT OF BASIC SCIENCES)

AGRICULTURAL CHEMISTRY
(BS131)
TABLE OF CONTENTS

INTRODUCTION .................................................................................................................................. 2
UNIT 1 BASIC CONCEPTS ............................................................................................................. 3
THE SEVEN FUNDAMENTAL S.I UNTS OF MEASUREMENTS ........................................................ 4
1.2.1 PHYSICAL AND CHEMICAL PROPERTIES OF MATTER ......................................................... 6
1.2.2 CHEMICAL CHANGE .................................................................................................................. 7
1.2.3 ELEMENTS ................................................................................................................................. 8
1.3.0 MIXTURES .................................................................................................................................. 8
1.3.1 HAMOGENEOUS AND HETEROGENEOUS MIXTURES .......................................................... 9
1.3.2 HETEROGENEOUS MIXTURE ................................................................................................... 9
1.3.3 METHODS USED FOR SEPARATING MIXTURES .................................................................... 9
CRYSTALLIZATION ........................................................................................................................... 10
CHROMATOGRAPHY ....................................................................................................................... 10
SIMPLE DISTILLATION ..................................................................................................................... 11
FRACTIONAL DISTILLATION ............................................................................................................ 11
1.3.4. TYPES OF MIXTURES ............................................................................................................ 12
Unit.2. ATOMIC STRUCTURE ........................................................................................................... 12
DEFINITIONS..................................................................................................................................... 14
2.2.2 IONIC OR ELECTROVALENT BOND: ...................................................................................... 15
2.2.3 Characteristics of Ionic compounds: .......................................................................................... 15
2, 2.4 SOLUBILITY OF COMPOUNDS (Ionic Compounds) ............................................................... 15
UNIT 3 THE PERIODIC TABLE ......................................................................................................... 19
UNIT 5.0 ACIDS AND BASES ................................................................................................... 24
UNIT 5 WATER. ................................................................................................................................. 31
6.0.0. COLLOIDS ............................................................................................................................... 41
UNIT 7.0 REDUCTION AND OXIDATION (REDOX) REACTIONS .................................................... 42
INTRODUCTION TO ORGANIC CHEMISTRY................................................................................... 46
Unit 1 organic chemistry ..................................................................................................................... 46
INTRODUCTION............................................................................................................................ 47
BASIC CONCEPTS ....................................................................................................................... 47
2.0.0 UNIQUENESS OF CARBON..................................................................................................... 47
4.0.0 HOMOLOGOUS SERIES .......................................................................................................... 53
RULES FOR IUPAC NOMENCLATURE ............................................................................................ 55
7.0.0. SUBSTITUTION REACTIONS ................................................................................................. 59
ORGANIC CHEMISTRY WORKSHEET I .............................................................................. 60
8.0.0. UNSATURATED HYDROCARBONS ....................................................................................... 61
9.0.0 ISOMERISM .............................................................................................................................. 62
11.0.0 FUNCTIONAL GROUP ORGANIC CHEMISTRY .................................................................... 67
12.0.0 CARBOXYLIC ACIDS (FATTY ACIDS) ................................................................................... 73
13.0.0 AMINES AND AMINO ACIDS .................................................................................................. 81
14.0.0 ALDEHYDES AND KETONES ................................................................................................ 90
15.0.0 CARBOHYDRATES ................................................................................................................ 93
16.0.0 PHENOLS ............................................................................................................................. 101
Introduction ...................................................................................................................................... 105
Unit objectives .................................................................................................................................. 105
Unit 3 Introduction to Environmental Management ........................................................................... 106

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INTRODUCTION
Welcome to Module I physical and inorganic chemistry. You will be introduced to basic concepts
which are applied in the field of Agriculture. In addition there are many chemical reactions that take
place in the soil or living organisms

You will study

1. Basic concepts in physical and inorganic chemistry applied to agriculture
2. Physical and Chemical reactions
3. Water – structure and properties.
4. Introduction to organic chemistry

MODULE OBJECTIVES
When you have worked through this module you should be able to:
1. State SI units and non - SI units of measurements.
2. State the base units of measurements.
3 Convert the difference kinds of units using conversion factors
4. Define basic concepts in physical chemistry and inorganic chemistry
5. Explain the different states of matter
6. Write and construct balanced equations
7. Define term mole in terms of Avogadro’s constant
8. Perform calculations, including the use of the mole concept, involving
i) Reacting masses
ii) Concentrations of solutions
6. Define acids, bases and salts as well as explain how buffer solutions control pH.
7. Explain qualitatively the variation in atomic radii and ionic radius.
8. Explain properties of water and how it supports life

ABOUT THIS MODULE

Unit 1. Basic Concepts. In this unit, you will be able to state the base units of measurements and
convert the different kinds of units using some conversion factors. You will be able to state the
three states of matter. You will also be able to distinguish between a physical change and a
chemical change.

Unit .2 Atomic Structure

In this unit, you will be able to state and identify the type of particles present in an atom

Unit. 3 Periodic Table

Arrangement of elements in the periodic table and their properties.

Unit.4 Acids, Bases and Salts

In this unit, you will be able to define and acid, base and salts. You will be introduced to the
buffer system

Unit.5 Water
In this unit, you will be able to state and explain the characteristics of water. You will be
able to state uses of water

Unit. 6 Oxidation/Reduction (Redox Reactions)

In this unit, you will be able to define oxidation and reduction in terms of electron transfer

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UNIT 1 BASIC CONCEPTS

INTRODUCTION

In this unit, you will look at basic concepts that will enable you work through this module. You will start
by looking at the SI units, derived units and conversions. You will then study matter. You cover the
following topics:
 Physical and Chemical change.
 Homogeneous and heterogeneous mixtures and
 Separation of mixtures.
You will work through 4 activities at different stages of the unit.

UNIT 1 OBJECTIVES

After you have worked through unit 1, you should be able to

1. State the SI units
2. Convert the different kinds of units.
3. Define matter.
4. State the different states of matter.
5. Distinguish between physical change and chemical change.
6. Define basic concepts in chemistry.
7. Explain homogeneous and heterogeneous mixtures.
8. Describe different methods of separating mixtures.

1.1.0 UNITS OF MEASUREMENTS

In this unit you will be introduced to SI units and non – SI units of measurements. You will be shown
how to convert the different kinds of units using some conversion factors.

Scientific measurements require that units are assigned to every measurement. The size of the
measured quantity can be only understood if the unit is given for that particular quantity. In the
chemistry laboratory you come across different types of instruments such as beam balances,
thermometers, measuring cylinders are commonly used for measuring such quantities as mass,
volume, temperature for experiments.

The metric system (International system of units S.I.) uses a variety of units for length, mass and
capacity. These units are mostly applied in the measurement of physical quantities in physics,
chemistry and other sciences. In order for you to understand the sizes of the quantity that you are
measuring, it is important to assign an appropriate unit for the measured quantity. It is important to
express the units in figures which the one we can easily understand. For example the age of an adult
expressed in seconds would give a very large figure which we can easily forget.

Activity 1
1. What units can you use when measuring?
The mass of a block (wooden)
The volume of water in a sprayer

The common units of length are kilometre (km), metres (m), centimetres (cm) and millimetres (mm).
The word ‘Cent’ comes from the Latin word ‘Centum’ meaning hundred. One centimetre is one
hundredth of a metre.

1cm =1/100m =1/102m =10-2m

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The word ‘Milli’ comes from the Latin word meaning thousand. A millimetre is a thousandth of a metre.

1mm =1/100m =1/ (10x10x10) m =1/103m =10-3 m

The word kilo is derived from the Greek word Khilloi meaning thousand.

1 kilometre (1km) =1000m=103m

1. The common units of mass are; tonne (t), kilogram (kg), gram (g) and milligram (mg).
2. The common units of capacity (volume) are litre (l) or millilitres (ml), decimetre cubed dm3 or
centimetre cubed (cm3).

The unit assigned to the measurement depends on the size of the physical quantity to be measured.
For instance, the SI unity for volume is decimetre.

THE SEVEN FUNDAMENTAL S.I UNTS OF MEASUREMENTS

The table 1 below depicts the physical quantities, S.I units and the symbols for the units.
Table 1

Physical Quantity Unit Symbol

Temperature Kelvin K
Time Second s
Length Metre m
Mass Kilogram Kg
Amount of substance Mole Mol
Intensity of light Candela Cd
Current Ampere A

The other forms of units are derived. They are obtained from the definition of the physical quantity. In
the definition, the seven base units of measurements are identified.

Energy = Mass x Acceleration x Distance = Kg x m/s2 x m = Kgm2/s2 = Joule

The joule is derived Kgm2/m2

What are the units for density?

At times the units used are non-SI (S.I Systeme International d’un
ites) units. They are applied when either the physical quantities being measured are very small or
quite large.

As an example, millimetres or centimetres cannot be used to measure the radius of the hydrogen
atom, instead Angstrom (Ao) is the unit that is used.

Below are some examples of non-SI units you will come across.
Table 2

Physical Quantity Unit Symbol Equivalent

Length Angstrom Ao 10-10 or 0.00000000001
Energy Calorie Cal 4.1840 Joules
Power Horse Power HP 745.700 Watts
Temperature Degree Fahrenheit oF F=9/5ToC+32

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Pressure Atmospheres or mm Atm 133.322 N/m2
Hg

From the table we can say,

1 Angstrom (Ao) =10-10m or 1m =1010 Ao
An Angstrom is a unit used for measuring small distances like the diameter of an atom.

Derived units

Physical Quantities S.I. Units Symbol for the Unit

Area Square metre m2
Volume (solid) Cubic metre m3
Density Kilogram/cubic metre or Kg/m3
gram/centimetre cubed
Volume (liquid) decimetre dm3

The following are equivalents of the units used for measuring length.
1cm = 10mm
1dm = 10mm
1m = 10dm
dm = decimetre

If you were to measure the volume of a liquid, the SI unit is cubic decimetre.
1 Litre = 1dm3
You can convert 1dm3 to m3
You know that 1dm =10-1m
(1dm) 3 = (10-1m) 3
Therefore 1dm3 =10-3m3

For most volume measurements in the laboratory the volume is quoted in cm3. You can convert 1dm3
to cm3.
You know that 1dm = 10cm
Taking cubes (1dm) 3 = (10cm) 3
1dm3 =103 cm3
1dm3 = 1000cm3

ActIvity 2

2. Convert 450cm3 to dm3

3. Calculate the number of cm3 in 0.25dm3

1.2. MATTER

This topic deals with the three states of matter as well as the difference between a physical change
and a chemical change. You will start by defining matter.
Matter includes all things that you can see or touch; though there are tiny particles which are so small
to be seen but you always interact with them. Examples of such are molecules, atoms or electrons.
These also have mass and occupy space. Matter can be defined as anything which occupies space
(has volume) and has mass.

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Matter exists in three states
(1) Gas
Gas particles move freely from one part of container to another part in random motion.
- The gas can occupy all space of container
- If someone is smoking in a corner of a room others will get the smell of the
smoke.

(2) Liquid
– Particles in a liquid are quite close to each other
They move from one part of the liquid to another.
The liquid can take the shape of the container due to free movements of the particles.

(3) Solid
- The particles are packed close to each other vibrating within the zero mean position.
- No displacement takes place. They are within the same position

The energy in a solid is transmitted from one particle to another. The solid can conduct heat energy
and electricity due to transfer of the energy from one particle to another.

Activity 4: Considering the three states in which matter exists and looking at the way the
particles exist in the three states.

State which one of the three states of matter can easily be compressed and which one cannot be
compressed.
Which one of the three states of matter would easily heat up (the whole body) if some heat energy is
applied to the three states of matter? Give reason.

1.2.1 PHYSICAL AND CHEMICAL PROPERTIES OF MATTER

A student studying agriculture should be able to distinguish clearly between the physical and chemical
properties of matter. There are many situations that we are faced with where we have to predict
whether a physical change has taken place or a chemical change is taking place.

A physical change can be specified without any reference to any other substance. Water as a solid,
water as a liquid and water as a gas (steam).

In a physical change no new substances are formed. When the physical change takes place, the
original substance can still be obtained by physical means.

Example
Heat heat
Ice from the fridge Water steam

(Solid)
Liquid (Gas)
Cool cool

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Following the forward arrows the change which takes place is

Solid Liquid Gas (change of state)

Reverse arrows

Gas Liquid Solid (change of state)

Other physical properties are:-

- Density – As the solid (water is being heated the density also reduces due to increase
in volume for the same mass of water except at 4oC where there is an enormous expansion of water).

Density is given as ℓ (rho) = mass

Volume
 rho is the symbol for density.
 Mass is the quantity of matter in a given sample of substance.

Activity .5

(1) Given a substance A with Mass = 10g and its Volume = 20cm3

Find the density of the substance.

(2) A rectangular block has the following measurements

Length (a) = 140cm

Breadth (b) = 100 cm
Height (h) = 50 cm
Mass (m) = 30g
What is the density of the block?

In a physical change, the type and amount of matter remains the same – only the density and/or
other physical properties change.

1.2.2 CHEMICAL CHANGE

In a chemical change an interaction occurs between the chemical substances. The substance(s)
formed as a result of the reaction has different chemical properties from those of the reacting
substance (reactants). New substances are formed. For example

H2 (g) + O2 (g) H2O (l)

The properties of H2 and O2 are different from those of water both physical and chemical
properties.

The product of the reaction is different in properties compared to the properties of hydrogen and
Oxygen.

Iron + water + Oxygen rust (iron oxide)

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1.2.3 ELEMENTS

These are the simplest forms of matter. A pure element has the same kind of atoms. Elements serve
as building blocks for all of the complex substances and simple ones.
The elements are given

For example: water has a combination of the element hydrogen and oxygen. Proteins and
carbohydrates have such elements as carbon, hydrogen and oxygen with such other elements as
nitrogen, sulphur like in proteins. Even if the substance is complex, it will be composed of a limited
set of elements.
You will also study the way the elements are arranged on the periodic table.

There are about 104 known elements on the Periodic Table. Only a few are of real interest in
chemistry. Others are highly radioactive and therefore need to be handled with great care. They
cannot be used in the laboratory for any form of experiment. For example: the uranium /plutonium
compound.

For a compound to be formed the elements combine in proportions that are in whole numbers and
constant according to Laws of Chemical combinations

1. Law of Constant composition: the law states that different samples of any pure compound
contain the same elements in the same proportion by mass irrespective of where the sample
has been found.

2. Law of Multiple Proportions: The law states that when two elements A and B form more
than one compound the ratio of the masses of elements of B that combine with a given fixed
mass of element A each of the compound can be expressed by small whole numbers.

1g of hydrogen combines with 8.0g of oxygen to form water.

What it means is that if we were to react 1.0g of hydrogen with 10.0g of oxygen, only 8.0g of oxygen
will be involved in the reaction. This is what we mean by a fixed ratio.

The 2.0g will be excess and remain unreacted.

1g hydrogen + 8g oxygen water Or

2g hydrogen + 16g oxygen water

Other examples for illustration

C(s) + O2 CO2(g)

This simply means one atom of carbon combines with one molecule of oxygen to form one molecule
of carbon dioxide. The ratio of combinations is thus fixed.

1.3.0 MIXTURES

In our everyday life we come across various types of mixtures for which the amounts to be mixed
might be specified or might not be specified.

You can mix 1 drop of kerosene with 1R of water or 10 drops of kerosene with 1 litre of water, the two
give a mixture of kerosene and water.
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1.3.1 HAMOGENEOUS AND HETEROGENEOUS MIXTURES

HOMGENEOUS MIXTURE: It is called solution. It has informed properties throughout. For example
a mixture of ammonium nitrate and water; every part of sample taken from the solution will show
same properties. These are such properties as composition or taste; colour.

A solution consists of a single phase.

Definition: A phase is any part of the system that has uniform properties and composition. for
example ink and water or milk (fresh)

In order to achieve one phase the two substances amount mix completely.

This can be done by

 stirring
 Or warming the mixture
 Or by agitation using a shaker

1.3.2 HETEROGENEOUS MIXTURE

This is a mixture which is not uniform in the distribution of constituent substances. A mixture of oil
and water will have the properties of water separately and the properties of oil.

The mixture can consist of two phases; for example oil and water. These when mixed together will
form two layers.
For a heterogeneous mixture the properties of the constituent components of the mixture are distinct,
one part of the mixture will give different properties from the other part of the mixture with a different
phase.
A pure substance undergoes phase changes. Take an example of water

Phase changes:

Solid (ice) Liquid Gas (steam).

Copper + Sulphur; you have a mixture of the two but when this mixture is heated, a chemical change
takes place.
The substance formed (copper sulphide) has different properties from those of copper and sulphur.

1.3.3 METHODS USED FOR SEPARATING MIXTURES

The methods of separating mixtures usually depend on how pure you would like the components to
be and also how fast you have to get the components. The equipment or pieces of apparatus will
depend on the method to be employed, as will be seen in the diagrams.
The following are some of the methods used for separating mixtures of substances:-

(a) Decantation – a quick method of separating the mixture which has two distinct phases
Examples: oil and water or sand and water
For this method to be applied the mixture should settle down to completely separated the constituents
of the mixture. The container is then tilted at an angle and slowly the liquid is poured out.

Disadvantage of this method

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The components of the mixture are not completely separated,
(i) Those that dissolve in water will be poured with the water into the other container
(ii) The particles that float on water are also poured out with the water.

The water that is separated from either sand or oil is not very pure.

(b) Filtration

It involves pouring the mixture on the filter paper placed in the funnel. The large solid particles are
separated from the mixture. The residue on the filter paper is discarded.

Disadvantages: Tiny solid particles can pass through the filter paper with the filtrate ‘Any soluble
material is not separated. It goes along with the filtrate

CRYSTALLIZATION

The impure solid is added to a small volume of hot solvent in which it dissolves. When cooled, the
pure solid crystallizes out and the impurities, which are present in small amounts, remain dissolved in
the solvent. The pure crystals can be removed by filtration under reduced pressure using a Buckner
funnel and flask. The crystals are then washed with cold solvent and dried
Conditions for good separation:

- The solvent should be carefully chosen

-
The pure solid should be readily soluble in the hot solvent and much less soluble in the cold
solvent.

CHROMATOGRAPHY

Paper chromatography can be used to show whether a substance is pure or contains some
impurities.

- A small spot of the substance in solution is put on a strip of filter paper

- The end of the filter paper is dipped into a suitable solvent.

Strip of filter paper

Spot with impurity

A separation occurs if the substance is impure as the solvent rises

up the strip of filter paper by capillary action. The compounds are
often identified by calculating the Rf values. These are compared
with values in the data book.

10
 dis tan cemovedbythespot
Rf value =
dis tan cemovedbythesolvent

- The Rf value depends on the type of solvent used.

- This technique requires only a very small amount of material
- Two way paper chromatography is a useful technique for separating complex mixtures of
similar compounds. Chromatography technique is often used in biochemistry for
separating mixtures of such molecules as amino acids or proteins.

Gas liquid chromatography (GLC) is the most useful technique for analysis of complex mixtures – it is
widely used to detect ethanol in breath in the new breath testing machinery.

SIMPLE DISTILLATION

This involves removal of a volatile solvent from a non-volatile solid (water + salt). The mixture in the
flask is heated and the volatile liquid evaporates. As the vapour passes through the condenser where
the cold water is passing through it is cooled and condenses.

- If the boiling point of the liquid is above 140ºC an air condenser is used. The air around the
condenser is used. The air around the condenser cools the vapour (contents of the tubes).

- If the liquid being distilled decomposes at a temperature close to its boiling point, the distillation is
done by steam distillation or under reduced pressure.

FRACTIONAL DISTILLATION

This is the process of separating mixtures of volatile liquids. The mixture components are separated
depending on their boiling points. The one which has lower boiling point is removed first from the
mixture. As the temperature increases other components are separated from the mixture.

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The columns in the distillation flask give different temperatures for the column.
Some examples in which this process is applied

(i) Fractional distillation of liquid air – the nitrogen is separated from liquid air and it is used in the
Harber process for production of ammonia used for manufactures of fertilizers.
(ii) Fractionation of crude oil at Indeni.

1.3.4. TYPES OF MIXTURES

The principal feature which differentiates one kind of mixture from another is the size of particles.
SUSPENSIONS
The large particles in a mixture are suspended within the mixture e.g. smoke in the air or dust
particles in the air.
Chalk dust forms a suspension in water.
There is an even distribution of large particles of one component of the mixture throughout another in
a suspension. To separate suspended particles from the mixture one can use the method of filtration.

- Let the mixture containing the suspended particles be made to settle by gravity

UNIT.1 SUMMARY:
In this unity you have been introduced to SI units commonly used in agriculture chemistry. You have
also been taught how to derive and convert these units.
You have learnt common symbols you will encounter in this course. You have been introduced to
basic concepts .In addition you have learnt about matter. The different ways of separation of matter
have also been dealt with.
At the end of this unit you should have completed 5 activities.
Having looked at unit 1 you are now ready to look at Atomic structure.
Unit.2. ATOMIC STRUCTURE

Introduction: Welcome to unit 2 which introduces you to atomic structure .You will be shown how the
electrons are filled for the given atomic number of an element. You will also be able to distinguish
between a cation and anion. Some more concepts will be introduced. You will look at the activity

12
series as well as factors that affect reactivity of elements. You will finish the unity with a discussion of
the types of bonds and their characteristics. There are some activities at different stages of the unity.

UNIT 2 OBJECIVES
When you have worked through this unit, you should be able to
 Draw and label the structure of the atom
 State and identify the type of particles present in an atom.
 distribute electrons for a given atomic number of an element
 Define concepts such as ions, compounds, solubility and so on.
 State the factors that determine the reactivity of elements.
 List elements according to their reactivity.
 State the Laws of Chemical combination.
 Define the mole in terms of the Avogadro constant.
 Define the terms relative atomic mass, isotopic mass, molecular and
formula masses of an isotope.
 Calculate the relative atomic mass of an element from isotopic masses.
 State important uses of isotopes in agriculture and other fields

2. ATOMIC STRUCTURE

The atomic structure gives an idea as to how

the elements behave chemically. The chemical
characteristics of the elements are determined
by the structure of the atoms of elements.
Atoms of an element consist of:

(i) The central part – the nucleus. The

nucleus consists of
(a) Protons with positive charge
(b) Neutrons with zero charge

(ii) Electrons orbiting around the nucleus, with negative charge.

Atoms of an element have the same number of protons; whereas the number of neutrons can vary (in
isotopes) e.g. 6C12 and 6C14
Carbon 12 has 6 neutrons and 6 protons; whereas carbon 14 has 6 protons and 8 neutrons.

The number of electrons can also vary for example when atoms are involved in a chemical reaction
and ions are formed.

20C and
40 40Ca2+
20

20Ca has: 20 protons

40

20 neutrons
20 electrons

20 Ca has: 20 protons}
40 2+

20 neutrons} more positive charge than negative charge

18 electrons}

IONS: These are negatively charged (anions) or positively charged (cations) atoms.
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Ions result from loss or gain in electrons by atoms. A difference in number of electrons (negative
charge) and protons (positive charge) leads to formation of ions. Whenever a chemical reaction
occurs electrons are either lost or gained, or shared between atoms. Any atom represented in the
form O2- or Mg2+ or Na+ is in ionic form
Positively charged atoms are called cations (cathode ions) whereas negatively charged ones are
known as anions (anode ions)

DEFINITIONS

(i) Electronegativity: An index of the ability of an atom of an element to attract an electron or

electrons i.e. to form an anion.

Cl + e- Cl- O + 2e- O2-

(ii) Electropositivity: An index of the extent to which atoms of the element tend to lose electrons
i.e. to form cations.

Ca - 2e- Ca2+

Metals are electron donors (electropositive). Decrease in negative charge

Non-metals are electron acceptors (electronegative). Increase in negative charge

The chemical activities (ability to lose or gain electrons) of elements depend on:-

 The number of electrons in the outer most shell of an atom – the valence electron. The more the
electrons there are in the outer shell the more energy is required to remove the electrons

 The distance of the outer most electrons from the positive charge (protons) in the nucleus.
Electrons are negatively charged whereas protons are positively charged. The further the outer
electron is from the nucleus the less the force of attraction between the positive and negative

 Number of electrons shielding the outer electrons from the protons. The outer electron more force
of repulsion if there are so many electrons shielding it. Electron – electron force of repulsion. It can
therefore easily be released from the atom. The atom becomes more reactive.

ACTIVITY1

You are given the following sets of elements

(i) Al, Na , Mg, K

(ii) Li, Na, K, Cs
For each set place the elements according to their reactivities.

2.1 COMPOUNDS.
You have to remember the Law of Chemical combination :
Law of Constant Composition (Law of Definite Proportions)
This states that different samples of any pure compound contain the same elements in the same
proportion by mass irrespective of where the sample has been found. The statement implies that
atoms of elements combine in fixed numerical ratios.
Thus water ( H2O) 11% H and 88.9% O by mass. A compound will have two or more elements
combined together in fixed ratio.
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Having stated the law of chemical combination you can now look at the types of combinations.

2.1.1 TYPES OF COMBINATIONS

2.1.2 IONIC OR ELECTROVALENT BOND:

This type of bond formed as a result of transfer of electrons from an electropositive atom e.g. K+ or
NH4+ to an electronegative atom e.g. Cl- or NO-3 PO43-. The bond formed consists of positive and
negative polarity.

When an atom loses or gains an electron

- The resulting ion is either positive or negative polarity

- It attains a duplet (2) or octet (8) number of electrons in outermost shell.
- It forms a stable structure and therefore can no longer lose or gain any more electrons

2.1.3 Characteristics of Ionic compounds:

 Since ionic compounds are polar (have both positive and negative polarities) in nature, they are
soluble in polar solvents (water). Some of the factors which determine their extent of solubility are:

 Temperature
 Nature of solvent – (polar or non-polar)
 Charge densities of cations and anions
 Surface area of the solute
Other factors that affect the solubility of solutes (ionic compounds) in an inorganic solvent (water):

- Charge density of cations and anions e.g. NO3- or PO43-; Na+ or Al3+
The higher the charge density the more force of attraction between positive and negative and so the
ions cannot easily be separated.
- Cation size e.g. sizes of Ba2+, Ca2+, Mg2+ ions.
Larger cations place the radicals at distant places in the molecular structure and therefore the
structure is stable compared to those that are close to each other which experience some force of
repulsion.

Explain how each of the following increases the rate of solubility.

- Temperature
- Nature of solvent
- Surface area of the solute
-

2, 1.4 SOLUBILITY OF COMPOUNDS (Ionic Compounds)

 Definition: Solubility of a solute in solvent is the maximum amount of solute in grams that
dissolves in 100g of solute at a given temperature
So here you have to consider three variables when the solute is being dissolved in a solvent:-
 The mass of the solute
 The volume of the solvent
 The temperature at which the solute is dissolving in a solvent.

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 A limit exists to the amount of solute that will dissolve in a solvent and when this limit is reached, the
solution is said to be saturated with the solute in the concentration of solute in a saturated solution is
the solubility of the solute in the solvent.

Unit of solubility: g/l or g/100ml.

The solubility of solutes in water varies widely between 0 g/l to 1000g/l depending on the chemical
nature of the solute.

Generally the solubility of solutes is governed by three rules:

(i) Solubility of most gases in water decreases with increasing temperature.

(ii) Substances tend to dissolve in solvents that are chemically similar to them.
(iii) Solubility of most compounds in water increases with increasing temperature.

(a) Polar compounds (ionic and covalent) dissolve readily in polar solvents

For example: Ammonia (polar molecule) dissolves in water (polar solvent)

NH4 NO3 (an ionic compound with charged ions; the NH4+ and NO3-)
NH4 and NO3-) form an aqueous solution in water. Ionic compounds which are hydrophilic (water
+

loving) are relatively insoluble in non-polar solvents (organic solvents).

(b) Un-polarized molecular solutes (many organic compounds) have low solubility in water but
dissolve in non-polar solvents like benzene, paraffin and petrol. Both solutes and solvents are
therefore hydrophobic (water hating).
(c) Those un-polarized organic substances that dissolve in water would have the following
characteristics:
(i) They are of low molecular masses e.g. methane (CH4) miscible with water
(ii) They have similar molecular structures to that of water (solvent).
For example, Sugars have – OH groups in their structures similar to that of water H – OH-; or
alcohols of lower molecular masses dissolve in water because they also have –OH groups in their
structures.

2.2.0 COVALENT BOND

The most predominant bond in nature, (Gases, plant materials, water, organic compounds,
biochemical), have molecules that are covalently bonded.
This type of bond is formed as a result of:-

(i) Atoms with same electro negativities (non-metals) bonding together through electron sharing.
Net polarity is zero in such compounds since the pair of electrons is shared equally.

16
(ii) Atoms of elements with different electronegativity sharing electrons.

The shared electrons in such bonding tend to be displaced towards the more electronegative atom,
giving a polarized covalent bond known as a dipole.

H+ + Cl- H: Cl or HCl
+ -
Since the chlorine is more electronegative than the hydrogen it draws most of the negative charge
towards itself creating a negative polarity. The hydrogen remains positive.

Other polar covalent molecules are:-

H2O, NH3 these have lone pairs of electrons (unshared electrons), which give polarity to such
molecules. The lone pairs also push the hydrogens at some angles giving different shapes for the
molecules
The molecules of ammonia, methane water have such shapes; pyramidal, tetrahedral and bent
respectively.

Some of the important covalently bonded compounds are:-

- Pesticides
- Nitrogen excretion products e.g. urea CON2H4
Uric acid C5O3N4H4
- Water (H2O)
- Atmospheric gases O2, N2, CO2
- Plastics (These are non – biodegradable and hence are a problem environmentally).

The covalent bond is the most predominant bond in nature.

2.3.1 Characteristics of covalent compounds:

 Since they are non-polar, they do not dissolve in ionic solvents. Organic solvents dissolve organic
solutes. Polar covalent compounds are soluble in polar solvents.
 Covalent compounds have low boiling and melting points. They are held together by weak
intermolecular electrostatic force of attraction.
 They do not conduct electric current, since their polarity is zero. They can conduct electric current
only at high voltage (lightening)

2.4 THE MOLE

The word mole is derived from the Latin word moles which means “amass’. The mole is the SI unit for
amount of substance in., is abbreviated as mol .It is defined as the amount of substance that contains
as many elementary entities (atoms, molecules, ions, or other particles) as there are in carbon-12
isotope.
Mole and Avogadro’s constant.
Definition: The amount of substance that contains Avogadro’s number of particles
Particles in the form of
- atoms
- molecules
- ions
17
Avogadro’s constant = 6.02 x 1023 particles

Mole =Mass⁄ (Gram atomic mass)

The atomic mass of an element is obtained from the constant from the periodic table. The atomic
mass of the element is obtained from the periodic table.

Gram atomic mass –atomic mass of an element converted or assigned a unit of gram. If the mass of
the substance is given in Kg kilograms or milligrams, it is converted to grams because we use gram-
atomic mass in the formula. This above formula is applied to elements.

If the moles of a compound have to be found then,

Moles =Mass⁄ Gram molecula mass

Molecular mass obtained from the sum of atomic masses of the element with their ratios of
combination.
Where molecules are covalently bonded compounds
e.g. CO2, H2O, CO(HH2)2, C6H12O6, O2, N2, CH4

Mole= Mass⁄ Gram formula mass

This is applied to electrovalently bonded compounds. For example

NaCl (Sodium chloride), NH4NO3 (Ammonium nitrate), CaCl2 (Calcium chloride). You can there be
asked either to calculate;
i) the mass of sample given the number of moles and molecular mass of the substance or
ii) the molecular mass of the substance
Molecular mass of water is;

Formula H2O H= (2 x 1) = 2
to be known H= (1X16) =16
first 18
1 and 16 are atomic masses of H and O respectively. The two and one are ratios of combination in a
water molecule.

ISOTOPES

Definition: These are atoms of an element with the same atomic number but different atomic masses
or atoms of an element with different number of neutrons.

The number of protons (atomic number) for any element will always be the same, but the number of
electrons may be different (e.g. in ions) or the number of neutrons may be different (e.g. in isotopes).

The atomic number (number of protons) serves, indirectly to distinguish an atom of one element from
an atom of another, because the number of electrons must equal the number of protons in an
electrically neutral atom.

The example below illustrate the types of atoms that we can get resulting from difference in number of
neutrons, number of electrons but same number of protons (atomic number)

For example, Sodium atom

Neutral atom isotope of sodium
18
11 Na 11Na
23 24

Properties of isotopes of hydrogen

Isotope No of protons No of electrons No of neutrons Atomic No Atomic mass

Protium (H) 1 1 0 1 1
Deuterim (D) 1 1 1 1 2
Tritium (T) 1 1 2 1 3

The atomic mass of an element

= No of protons + No of neutrons

Atomic No = no of protons

QUESTIONS

1. Distinguish between a covalent bond and an ionic bond.

2. Draw structures to show how the two types are formed.
3. Give examples of compounds which are

(i) covalently bonded

(ii) electrovalent bonded

4. What is the difference between a mass number and its actual atomic mass?
5. The element Eu occurs naturally as a mixture of 48% Eu-150 and 52% Eu-153.
Calculate the average mass of europium (Eu).

UNITY 2 SUMMARY

In this unity, you have been able define the mole. You have been introduced to isotopes and how to
calculate isotopic masses. In addition you have looked at the importance of isotopes. You should
have worked through one activity.
You can now look at wave mechanics.

UNIT 3 THE PERIODIC TABLE

INTRODUCTION

Welcome to inorganic chemistry. The periodic table will be discussed. At the end of the unit you will
work through bonding including ionic and covalent bonds.

MODULE.3. OBJECTIVES

When you have worked through this module you should be able to

1. Define basic concepts in inorganic chemistry

2. Write the configuration of an element given the atomic number
3. Define the period.
4. Describe the reactions of elements with oxygen and water
19
5. Describe the use of lime in Agriculture
6. Define ionic bond and covalent bond
7. Explain thermal stability of ions
8. Explain the properties of covalent and ionic bonds
9. Define electropositivity and electronegativity
10. Mention examples of covalently and electrovalently bonded compounds

3.1.0. THE PERIODIC TABLE OF ELEMENTS

The periodic table is an arrangement of all the chemical elements in order of increasing atomic
number. Elements with similar properties (i.e. the same chemical family) are placed in the same
vertical column known as groups. These groups are from 1 to 8 or 0.
The horizontal rows are known as periods. Physical properties such as ionization energy, electron
energy, electron affinity, melting and boiling points are related to election arrangements. Properties of
elements are periodic functions of their atomic numbers.

The table arranges the elements in definite patterns in relation to electronegativity and
Electropositivity. It also places the elements in their correct order of atomic numbers. Elements on
the periodic table are placed in
- Groups
- Periods
- Blocks

3.2.1. Groups of elements

- Group A – there are eight groups – from 1A to 8A or 0 (S and P blocks)

- Group B there are 10 groups the d block and with 14 groups of elements

3.2.2. Characteristics – The Elements in a group have the following characteristics:-

- They have the same number of electrons in the outer shell

- They have similar chemical characteristics (they are a family)
- Down each group elements become more reactive.

Reasons:- Down each group the number of shells increases by one. This increase the distance from
the nucleus to the outer shell (reduce shell).

- More electrons shield the outer electrons.

3.2.3. Periods of Elements

They are seven periods on the periodic table. These are horizontal rows with period 1 consisting of
the elements hydrogen and helium. Elements in the same period have the same number of shells.
Period 1 1 Shell
Period 2 2 Shells
Period 3 3 Shells
Period 4 4 Shells
Period 7 7 Shells
- Across each period the atomic number increases by 1.
- The electronegativity of elements increases across each period. Elements on the left hand
side of the periodic table are electron donors (in each period) whereas those on the right
hand side are electron acceptors. Across each period element become less metallic.

20
Definitions:

Element – a substance comprised of atoms of the same atomic number (number of protons) in the
nucleus. The periodic table arranges elements in a definite patter in relation to their electro negativity
and electro positivity.

21
Ionization energy: amount of energy required to remove an electron from a neutral atom
to infinite is known as the first ionization energy.

Core electrons – Electrons found in completely energy levels. The following are some of the factors
which influence the reactivity of elements.

- The number of electrons in the outermost shell (the valence electrons) of an atom.
- The distance of the outer shell electrons from the nucleus for electroposive elements.
- The number of electrons shielding the outer electrons.

The periodic table places the elements in their correct order of atomic number the ionization energy
increasing across each period and decreasing down each group, for the electropositive elements.

Elements on the periodic table are classed according to their physical properties.

→ Metal - conductors of electric current

→ Metalloids - semi-conductors of electric current

→ Non-metals - non-conductors of electric current

The elements on the periodic table are placed (i) in group columns (Groups 1 to 0 across the table),
and also in period (period 1 to 7 down the table in rows).

The elements in the same group behave similarly in chemical reactions. We would take an example
of for instance group 1 elements which lose one electron during the chemical reaction with a non-
metal. All group 2 elements lose two electrons (valence electrons) during a chemical reaction. Group
3 lose 3 electrons. Group 7 elements gain 1 electron to have an octet (8) number of electrons in outer
shell; a stable or core electrons, group 6 elements gain 2 electrons in the outer shell to attain a stable
or octet number of electrons in the outer shell.

Once a duet (duplet) or octet number of electrons in the outer shell has been attained none of the two
or eight electrons can be released by an atom. The atom attains a stable configuration. The ion
formed can no longer take part in other chemical reactions. It behaves like an atom of a noble gas
which has two or eight electrons in outer shell (inert or inactive elements). Na+ 2 8 has similar
electronic structure like that of neon (Ne 2 8)

22
Hydrogen gains an electron-from a metal element the hydrogen ion with two (duet or duplet number of
electron. It has the same structure as that of helium, an inert gas. Hydrogen atom behaves like a
non-metal.

The hydrogen ion H+ is also known as a proton because it has 1 proton, no electron and no neutron.
It is for this reason that hydrogen is considered to behave as a metal – electron donor and a non-
metal – electron acceptor and that is why it is found in the middle of the periodic table. Check on the
position of hydrogen on the periodic table.

Valences of hydrogen +1 (in group 1) when it donates an electron

Or -1 (in group 7) when it receives an electron

3.2.4. BLOCKS OF ELEMENTS

The elements on the periodic table are also place in blocks. The shape of the periodic table gives the
different kinds of blocks to which the elements belong.

The blocks to which the elements belong are

- The s block s for sharp

- The p block p for principal
- The d block d for diffuse
- The f block f for fundamental or fine

The chemical reactivities of the elements depend upon the following factors:

(i) the distance of the outer electron from the nucleus – electrons are negatively charged
whereas protons are positively charged so there is attraction between positive and
negative charge.

The further the outer electron, the less the force of attraction. The outer electron is further away from
the nucleus less energy is required to remove it from the shell to infinite. Here infinite simply means
some distance where the positive charge = 0

23
Atom A with two shells

Distance of outer electron is close to the nucleus. The electron is closer to the nucleus (the positive
charge) than in atom B. The less energy is required to remove the electron in atom B. So atom B is
more reactive than atom A. The ionization energy of atom B is lower than that of A.
Increasing electro negativity

K 2 8 8 1

Na 2 8 1

M 2 8 2

More energy is required to remove electron in the outermost shell of Mg than removing one electron
in the outer shell of Na.

Increased nuclear charge in Mg draws the electrons closer to the nucleus and hence more energy
required removing the electrons than in Na. Sodium is therefore more reactive than magnesium.
Increasing electro positivity

*The outer electron is far from the nuclear positive charge in K. It can easily be released from the
outer shell.

*More negative charge shields the outer electron. The electron gets repelled by negative charge.

*Potassium is therefore more reactive than sodium.

Period 2
2 8 1 / 2 8 2 / 2 8 3Increasing electro negativity

- More affinity for an electron from infinity in the fluorine atom due to increased nuclear
charge.

- Less energy is required to bring in one electron of fluorine from infinity into outer shell.
- Fluorine is more reactive than oxygen.
More electro positive

- More energy is required to bring in an electron from infinity into the outer shell of chlorine due
to

(i) distance of outer shell from the protons

(ii) more force of repulsion is experienced
(iii) electron shielding

UNIT 4.0 ACIDS AND BASES

INTRODUCTION

Well come to unit 5, the unit starts with Morden definitions of Acids and Bases.
You will be introduced to types of Acids and Bases. In addition neutralisation reaction
(the reaction between an acid and a base) will be introduced.
24
Later the Bronsted-Lowry definition of acids and bases will be discussed. Towards

the end of the unit you will look at the pH concept and Buffer system.

MODULE 4 OBJECTIVES

After you have worked through this module you should be able to

1. Define Acids and Bases in aqueous solution.

2. Discuss the neutralization reaction
3. Define Acids and Bases in terms of electrons – Bronsted-Lowry definitions
4. Explain the terms pH, Kw, pKa and pKb
5 Calculate (H+) and pH values for strong and weak acids
6 Derive the auntionilization constant of water
7 Explain how buffer solutions control pH
8 Mention at least five uses of the Buffer solution
9. Calculate the pH of buffer solutions given appropriate data

ACIDS AND BASES

According to Arrhenius:

An acid is a substance that increases the concentration of hydronium ions (H3O) in an aqueous
solution.

A base is a substance that increases the concentration of hydroxide ion OH-

4.1 Acids

In general acids are molecular substances that produce hydronium ion by reaction with water.
Hydrogen Chloride is an acid because when it is dissolved in water it reacts with the solvent to
produce H3O+. If we use H+ as H3O+ leaving out molecule of water that carries H+

HCl aq + H2O → H3O+(aq) + Cl-

HCl aq → H+(aq) – Cl – aq

An aqueous solution of hydrogen chloride is called hydrochloric acid. HCl is a strong electrolyte; its
reaction with water is complete. Because a mole of HCl releases a mole of H3O+, therefore,
hydrochloric acid is strong acid.

These are also many acids that are weak electrolytes. Acetic acid, HC2H3O2 is an example. Recall

H C2 H3 O2 (aq) + H2O ↔ H3O+aq + C2 H3 O2 – (aq)

Or

H C2 H3 O2 (aq) ↔ H+ (aq) + C2 H3 O2 – (aq)

25
This is equilibrium and in a solution of H C2 H3 O2 only a small fraction of the solute is dissolved into
ions. This means that the concentration of H3O+ in the solution is low. As result, acetic acid and other
acids that are weak electrolytes are called weak acids

Notice that in the formula for acetic acid, H C2 H3 O2, Hydrogen appears twice once at the beginning
of the formula and once in the middle. In writing the formula for an acid, its common practice to write
the acidic hydrogen’s, those that are able to transfer to water molecules to give H3 O+ ions – First in
the formula other Hydrogens that are not acidic are written later. Even though the acetic molecule
contains four hydrogen atoms only are of them is able to react with a water molecule to form H3O+.
Both HCl and H C2 H3 O2 are able to furnish only one hydrogen ion (or proton) per molecule of the
acid. Such acids are called monoprotic acids. These are also many acids that are able to furnish
mole than one proton per molecule of the acid. As a class, they are referred to as polyprotic acids.
For example,
H2 S O4 and H3 PO4 sulphuric and phosphoric acid

Sulphuric acid is also called a diprotic acid because each molecule of it is able to give up two protons.
This happens in two steps

Step 1 H2 SO 4 → H+ + H S O4-

Step 2 H S O4- ↔ H+ + S O42-

Similarly, phosphoric acid, which is an example of a triprotic acid, dissociates in three separate steps

Step 1 H3 P O4 ↔ H+ H2 P O4-

Step 2 H2 PO4 ↔ H+ + HPO2-

STEP 3 HPO4 ↔ H+ + PO4 3-

Notice that the second step in the dissociation of H2SO4 is equilibrium only about 10% of the HSO4- is
actually dissociated. Despite this, sulphuric acid is considered strong acid because the first
dissociation step is complete. Phosphoric acid, which is used in manufacturing fertilizers and
detergents and various soft drinks such as colas, is a weak acid because all three of its dissociation
steps are equilibrium that are reversible.

These are other substances that do not contain hydrogen, yet still produce acidic solutions when
dissolved in water. For example, carbon dioxide when dissolved in water (in a carbonated beverage
for example)

CO2 + H2O ↔ H2 CO2

The compound H2 CO3 is called carbonic acid; it is a weak diprotic acid that dissociated in two steps.
This particular acid, incidentally, is responsible for the large limestone caves that exist in various parts
of the world. Ground water, made acidic by CO2 dissolved in it from the atmosphere

CaCo3(s) + H2 CO3(aq) → Ca2+(aq) + 2HCO3-(aq)

26
4.2 BASES

There are two kinds of bases ionic hydroxide and molecular substances that react with water to
produce OH-. Sodium hydroxide and calcium hydroxide are typical ionic hydroxides. In the solid state
they consist of a metal ion and hydroxide ion and they dissolve in water and dissociate

Na OH (s) — Na + aq + OH (aq)

Ca (OH)2 → Ca2 + aq + 2OH- (aq)

Ionic metal common molecular substance that is a base is ammonia, NH3. It reacts with water in
equilibrium

NH3(aq) + H2O ↔ NH4+(aq) + OH – (aq)

In this case, a proton is transferred from a water molecule to an ammonia molecule.

This reaction is indicated as equilibrium because only a small fraction of the NH3 in the solution is
present as NH4+ and OH- at any given instant.

Ammonia is therefore a weak electrolyte. It is said to be a weak base because its solution contain
only relatively small concentration of OH-

Molecular bases are weak bases.

4.3 NEUTRALISATION

The most important reaction that acids and bases undergo is their reaction with each other, a reaction
called Neutralization in aqueous solutions, the neutralization reaction between a strong acid and a
strong base takes the form of the net ionic equation.

Mg (OH)2 + (S) + 2H+ → Mg2+ (aq) + H2O

Bronsted – Lowry acids and Bases

NH3(a) + HCl(g) → NH4 Cl(s)

NH3 (aq) + HCl (aq) → NH4 Cl(s)

Definitions of Acids and Bases by Bronsted and Lowry

An acid is a substance that is able to donate a proton (hydrogen ion H+) to some other substance and
a base is a substance that is able to accept a proton from an acid.

In short: An acid is a proton donor

A base is a proton acceptor

27
Based on this definition the above equation can be explained.
Since a proton is transferred from the HCl to the NH3, this is clearly an acid – based reaction in the
Bronsted- Lowry sense. In the reaction HCl is the acid because it is a proton donor, and NH3 is the
base because it is a proton acceptor. Thus, under both the Arrhenius and Bronsted-Lowry definitions
HCl is an acid and NH3 is a base.

The reaction between HCl and NH3, illustrates the more general nature of Bronsted-Lowry definition of
acids and Bases. Any reaction in which a proton is transferred from one particle to another is an acid-
base reaction; hydroxide ion and hydronium do not have to be involved. In fact acid-base reactions
do not even require a solvent.

4.5 THE IONIZATION OF WATER AND THE pH CONCEPT

H2O + H2O H3O+(aq) + OH-(aq)

As earlier stated this is an auntionization reaction. (two molecules of the solvent react with each other
to form ions).

Since auntionization is equilibrium we can write an equilibrium expression for it

K = [ H3O+][OH-] = [ H3O+][OH-]
[H2O][H2O] [H2O]2
The molar concentration of water which appears in the dominator of the expression is very nearly
constant (B556 m) in both pure water and dilute aqueous solutions.

K x [H2O]2 = [ H3O+][OH-]

Let Kw = K x [H2O]2

Therefore Kw = [ H3O+][OH-]

Is the product of ionic concentrations Kw is called the ionic product constant for water or ionization
constant or dissociation constant of water.

At 21o C Kw = 1.0 x 10-14

Kw = [H+] [OH-]

H2O ↔ H+ + OH-

One mol of water of H+ and

One mol of OH- at equilibrium
[H+] = [OH-]
x = [H+] = [OH] KW = x2

But KW = 1.0 x 10-14 x2 = 1.0 x 10-14

x = 1.0 x 10-7

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

28
Whenever the hydrogen ion once equals the hydroxide ion as it does in water, the solution is said to
be neutral.

In aqueous solution of an acid you will be interested in the H+ from the acid. In these cases it is
almost always safe to assume that essentially all the H+ in the solution comes from the dissolved acid.
In other words, it is usually safe to assume that the dissociation of H20 contributes to negligible
amount of H+ to the solution. This is because the presence of H+ from the acid shifts the equilibrium
to the left. Therefore, the amount of water that dissociates in the solution of an acid is even less than
10-7M

4.5.1 THE pH CONCEPT

1
PX = log x
= -log x
Similarly if we wish to specify the hydrogen ion concentration in a solution

We speak of pH

pH = log 1 = - log (H+)

(H)

In a solution where the hydrogen concentration is 10-3m, we therefore have

pH = -log (10-3) = -(-3) = 3
pH = 3
pOH = log 1 = - log (OH-)
(OH)
Just as the H+ and OH- and ion concentrations in a solution are related to each other so also are the
pH and pOH

Log KW = log (H+) + log (OH-)

Multiply by -1
-log KW = - log (H+) – log (OH-)

It follows our definition

pKW = -logKW

PKW = PH + POH = 14

In a neutral solution (H+) = (OH-) = 10.7

pH = pOH = 7
In a neutral solution pH = 7.0. In an acid solution the hydrogen concentration is greater than 10-7 m.
For example 10-3 M , pH is less than 7.0. By the same token in basic solutions the (H+) is less than 10-
7 M. 10-10M and pH is greater than 7.0

[H+] [OH-] pH pOH

Acidic solution > 10-7 < 10-7 >7 >7

Neutral solution 10-7 10-7 7 7

Basic solution < 10-7 > 10-7 >7 <7

29
Many common substances all either acidic or basic and their degree of acidity or basicity is
conveniently expressed in terms of pH

ACTIVITY 2

1. What is the pH of A 0.002 M HCl

pH = - log (H+) = - log (2.0 x 10-3)
= 2.70

4.6.0 BUFFERS
A buffer solution keeps its PH approximately constant when small amounts of an acid or alkali are
added. There are two types of buffer
Acidic buffers keep the PH over 7

When small quantities of a strong acid are added, they are neutralized by the weak base while small
quantities of a strong base are neutralized by the weak acid. Such solutions are said to be buffers
because they resist significant changes in the PH.

A buffer whose PH is less than 7 generally can be prepared by mixing a weak acid with the salt of the
weak acid e.g. acetic acid and sodium acetate. An alkaline buffer A buffer whose PH is greater than 7
generally can be prepared by mixing a weak base with the salt of that weak base – e.g.
Ammonia/Ammonium chloride. When H+ or OH- are added to an acetate – Acetic acid buffer, the
following neutralization take place
H+ + C2 H3 O2- → H C2 H3 O2
OH- + H2 C2 H3 O2 → H3O+ + C2 H3 O2-

Similarly for the NH3, NH4 Cl basic buffer we have

H+ + NH → NH4+
OH- + NH4 → H2O + NH3

UNIT SUMMARY
In this unit you have worked through the definitions of Acids and Bases according to Arrhenius as well
as Bronsted-Lowry. You have been introduced to neutralization reaction and ionization of water. The
pH concept as also been discussed. In addition you have been introduced to weak acids and bases.
The Buffer system has been explained in detail. Finally, you have looked at the practical uses of the
Buffer have been mentioned.

30
UNIT 5 WATER.

INTRODUCTION
Welcome to unit 6. You will look at the structure of water then proceed to look at properties of water.
You will also discuss the importance of water to life.

UNIT OBJECTIVES
After you have worked through the unit you should be able to

1. draw the covalent structure of the water molecule and assign the polarities
2. State and explain the properties of water
3. State the problems of hard water.
4. Describe the importance of water to plant life.

5.0.0 WATER

Water is major constituent of both plants (over 90% in annuals) and animals (typically 60 to 70% in
vertebrates). And hence the saying water is life. It has so many uses more especially in the field of
agriculture.

5.1.0. STRUCTURE OF WATER MOLECULES

Water molecules are covalently bonded (H-OH). Due to presence of lone pairs of oxygen, the water
molecules are polarized (polar) with a partial negative charge on the oxygen atom and partial positive
on the hydrogen atom.

_ -

O OR O Structure of water molecule (polar)

H + H HS+ S
+ H

Because of the polarization of the O-H bond in water molecules, the partial negative charge on the O
atom of each molecule will be attracted to the partial positive charge on the nearest neighbouring
water molecule, giving a network of hydrogen bonds between the molecules of liquid water.

Hydrogen bonds
In water molecules

31
32
Each of these clusters (with cage-like structure) is continually exchanging water molecules with other
clusters and with the pool of unbonded molecules. This flickering cluster structure is therefore
dynamic in contrast to the static structure of crystalline solid.

The hydrogen bonds are important

 For existence of life on earth
33
 In maintaining the shapes and activities of vital biochemical molecules such as enzymes and
nucleic acids.
NB: Although the hydrogen bonds are stronger than other intermolecular forces (van der Waals
bonds) they are only 1/24th as strong as an O-H covalent bond.

With the hydrogen bonding between adjacent water molecules extending uniformly throughout liquid
water; it would be solid at room temperature.

Hexagonal structure of ice (three dimensional)

 Hydrogen O oxygen

Water is not a solid at room temperature. It is thought to be made up of a large number of small
clusters (or ice bergs) of hydrogen bonded water molecules separated by volumes containing free
unbonded molecules.

34
5.1.3. THERMAL PROPERTIES FO WATER

Effect of heat on liquid: causes rise in temperature and random movement of the molecules (rapid
and then free).

In liquid water most of the molecules are held firmly together by hydrogen bonds. As such a large
amount of heat is required to overcome the intermolecular bonding and allow the molecules to move
more rapidly. Because of these strong intermolecular forces, the specific heat of the liquid water is so
high compared to that of less structured liquids.

Definition: Specific heat of liquid water is the amount of heat energy required to raise the temperature
of 1g of water by 10C.

Specific Heaters of selected Molecular Substances

Compound Molecular weight Specific Heat J/g/0C

Water H2O 18 4.2
Ethanol C2H5OH 46 2.2
Acetone CH3COCH3 58 2.1
Carbon Tetrachloride CCL4 154 0.8

Also when ice melts, or liquid water evaporates, large quantities of heat energy is required to break
the hydrogen bonded structure for the molecules to escape and move more freely. This leads to high
temperatures for such changes (latent heat of melting and latent heat of vaporization) compared with
other molecular substances.

TABLE
Comparison of thermal properties of some of molecular substances.

Molecule Melting Point 0C Boiling point 0C Latent heat of Latent heat of

Melting (J/g Vaporization (J/g)

Water 0 100 334 2260

Ammonia -78 033 332 1374
Ethanol -117 79 105 854
Acetone -95 56 98 521
Carbon -23 77 18 198
Tetrachloride
Because of its high specific heat capacity, water is a very good temperature ‘buffer’ absorbing or
loosing large amounts of heat without excessive variation in temperature.

Significance:

Helps to:-

 Maintain the temperatures of warm blooded animals close to an optimum value as required.
 Control the temperatures of soils. The surface layers of a bare dry soil can experience
enormous daily fluctuations of temperature (30 to 40 o C), 2441 J of heat is also lost from the
skin or leaf surface.

35
The high latent heat of vaporization of water accounts for the serious burns or scalds caused by the
exposure of the skin to steam. The condensation of each gram of steam releases 2260J of heat (100
o C).

OTHER PROPERTIES OF WATER

(a) WATER AS A SOLVENT

It is an excellent solvent for the following three groups of biologically important solutes:

(i) Organic solutes with which water can form hydrogen bonds.

These include:

 Amino acids
 Low molecular weight carbohydrates and proteins which contain hydroxyl groups
 Amine or carboxylic acid functional groups

Water forms colloidal dispersions with lager protein and carbohydrate molecules (e.g. cytoplasm).

Also water wets or adheres to solid substances such as glass, cotton and clay minerals which carry
hydroxy1 groups on their surfaces.

(ii) Charged Ions

Ionic salts dissolve readily because water molecules (partially charged) orientate themselves by
attracting the positive charge and pull them into solution where they exist as hydrated cations.

Water molecules also become attached to fixed charges on the surfaces of plant cell walls, cell walls,
cell membranes and soil particles giving tightly bound layers of water a few molecules thick.

(iii) Small Molecules:

e.g. atmospheric gases, which can fit into holes in the open, cage-like structure of liquid water. Water
therefore is a suitable medium for the transport of organic molecules such as:

36
  Sucrose in blood and phloem
 Nutrient ions from root to leaf in the xylem
 Atmospheric gases i.e. movement of such gases as O2 to sites of respiration

Definitions:

Hydrophilic Substances:- substances that dissolve in or bind water. Water loving substances.

Hydrophobic substances:- substances that neither dissolve nor bind water; ie water hating
substances. E.g. hydrocarbons, halogenated hydrocarbons, greases, fats, oils.

Amphipathic substances:- substances which contain both hydrophobic an hydrophilic groups eg.
Synthetic detergents.

37
5.1.4. VOLUME CHANGES IN ICE AND WATER

Ice expands with rising temperature but at its melting point there is a large and sudden contraction in
volume (about 9%) followed by a more gradual contraction between 0 and 40 C, the liquid reverts to a
more conventional steady expansion with increasing temperature.

The reason for this unusual behaviour of water is that the crystal structure of ice is a rather open,
cage-like lattice (as in the icebergs of liquid water). When the crystal structure breaks down on
melting, individual water molecules are more mobile and can approach one another more closely,
thereby occupying a smaller volume. Water cooler than the critical temperature (40 C) is less dense
and remains at the surface where ice forms first. This property of water is very important for the
survival of aquatic organisms in cold climates.

5.1.5. TENSILE STRENGTH AND VISCOSITY OF WATER MOLECULES

Viscosity of a liquid is a measure of its ‘stickiness’’ as it flows through a column. It determines the
rate at which the liquid will pour from the spout or flow along a pipe.

Tensile strength and viscosity are very important in the movement of water in animals, plants and
soils. The unusual tensile strength or cohesion of water columns in the xylem (due again to
intermolecular hydrogen bonding) means that water can be drawn to the tops of tall trees by
transpirational pull alone. In spite of its strong intermolecular hydrogen bonds, water has a moderate
viscosity compared to other molecular liquids, permitting rapid mass flow through pipes (irrigation
pipes, blood vessels, soil pores, xylem conduits) in response to modest pressure gradient.

of a range of liquid substances

38
Compound Viscosity (Centipoises) Temperature (0 C)
Acetone 0.316 25
Carbon Tetrachloride 0.969 20
Water 1.002 20
Ethanol 1.200 20
Glycerol 1.490 20
Mercury 1.554 20
Light machine oil 113.8 15
Heavy machine oil 660.6 15

The rapid fall in the viscosity of water with rising temperature also has practical consequences e.g.
tropical soils drain more rapidly than temperate soils.

Influence of Temperature on the Viscosity of Liquid Water

Temperature (0 C) 0 5 10 15 20 25 30 35

Viscosity (Centipoises) 1.787 1.516 1.306 1.138 1.992 0.890 0.798 0.719

The transparency of water ensures a supply of light for photosynthesis to the submerged plants and
algae; similarly the transmission of light through cytoplasm means that energy for photosynthesis can
be captured by several layers of cell in the mesophyll of the leaves of plants.

5.2.0. FUNCTIONS OF WATER IN LIVING TISSUES

 A medium for many biochemical reactions

 A medium for excretion processes

Transportation of inorganic nutrients, photosynthate gases, and hormones is when in aqueous

solution.
Evaporation of water can control the temperature of the skin or leaf.
Soil nutrients are available to plant roots only when dissolved in soil water.

Other Roles of Water

 Pesticides are applied to crops or livestock as aqueous solutions or suspensions

 For irrigation and fish culture
 In soil formation and erosion

In agriculture production:

(a) It is estimated that between 35 and 45 metric tons of water are required for the production of
each kilogram of beef. This includes fodder production, dipping, carcasses preparation, as well as
physiological requirements of the animal.

(b) Of the soil moisture absorbed by a maize crop, 98% is lost by transpiration; the remainder is
retained in the plant body and only 0.2% is chemically broken down in photosynthesis.
39
5.3.0. USES OF WATER

Water has many uses and for each it must achieve certain standards of purity e.g. it is necessary for
irrigation water to contain low concentrations of salts so as to avoid the build-up of soil salinity under
conditions of rapid evaporation.

For industrial and household (washing) purposes, ‘soft’ water with a low dissolved salt content is
preferred. ‘Hard’ water containing significant concentrations of Ca, Mg, Fe salts (particularly
carbonates and bicarbonates) normally originates from limestone catchments or from boreholes
receiving large quantities of leached salts.

5.4.0. PROBLEMS CAUSED BY HARD WATER

 Over a period of time, calcium salts from hard water accumulate as deposits of ‘fur’ or ‘scale’ in
boiler pipes or kettles, reducing water flow and decreasing the efficiency of heating.
 The salts in hard water also cause the precipitation and inactivation of detergents.

These problems can be overcome by passing water through an ion exchange or by use of special
synthetic detergents.
.
Waste water can be purified by the following methods:-

 Using resins (deionization of water)

 Electro dialysis
 Reverse osmosis

ACTIVITY

(1) Explain the structure of water molecules

(2) Discuss some of the important properties of water molecules which lead to sustenance of life
on earth.
(3) Outline some of the functions and roles of water in living tissues and field of agriculture.

(4) Explain briefly how each of the following factors influences the solubility of a fertilizer in water.

 Temperature
 Surface area
 Charge density
 Cation size
 Nature of solvent

(5) What would be the consequences on the properties of water and for plants and animals if the
earth moved closer or further away from the sun?

40
6.0.0. COLLOIDS

Matter exists in the colloidal state when it divided into small particles of diameter 10-9 to 10-6 meters.
Colloids are therefore defined by the size of their particles, which may consist of very large molecules
(macromolecules) or clusters of molecules or atoms. Colloidal systems consist of matter in the
colloidal state (the dispersed phase) spread uniformly throughout a dispersion medium. Both the
dispersed phase and dispersion medium can exist in each of the three states of matter.

Dispersed phase Dispersion medium Colloidal system Example

Liquid Gas Liquid aerosol Fog

Solid Gas Solid aerosol Smoke, dust

Gas Liquid Foam Soap lather,

Extinguisher foam

Liquid Liquid Emulsion Milk

Solid Liquid Sol, Paste Toothpaste

The most important kinds of colloidal systems in environmental chemistry are sols and emulsions.

6.1 COLLOIDAL SYSTEMS

The three distinct classes of sols and emulsions are:-

(a) True solutions of macromolecules: Most familiar examples of this type of sol are solutions of
hydrophilic macromolecules (proteins, carbohydrates) in water. The cytoplasm is a complex

41
 solution of many different macromolecules, predominantly proteins. If the dispersion medium
is not water e.g. rubber in benzene, the dispersed phase is called lyophilic; solvent loving.

Solutions of colloids have such characteristics as:-

 High viscosity – This accounts for the name colloid which means glue-like.
 Dialysis – Macromolecules in solution do not pass through the pores of the dialysis
membranes. Dialysis is therefore a useful technique in biochemistry for separating
macromolecules from others, usually inorganic solutes.

(b) Association Colloidal Systems: formed when a number of amphipathic molecules (containing
lyophobic and lyophillic groups) cluster together to form miscelles of colloidal dimensions. Soaps and
detergents form association colloidal systems in water.

(b) Colloidal Dispersions: The dispersed phase consists of atoms or molecules clumped together
into particles of colloid size. These are not true solutiosn because the dispersed phase is
normally strongly lyophillic; however, the clumps are not forced together by the solvent to give
a precipitate because they ten to accumulate (charged ions) from solution on their surface.
This results into strong repulsion by the charged clumps and they remain in suspension. The
hydrated iron oxide/water sol is an example of a colloidal dispersion which can easily be
demonstrated in laboratory.

UNIT 7.0 REDUCTION AND OXIDATION (REDOX) REACTIONS

INTRODUCTION

In this unit you will be introduced to different definitions of redox reactions. You will discuss rules for
assigning the oxidation numbers. In addition you will look at Redox reactions in soils. You will end by
looking at the equations based on oxidation of pyrites.

42
UNIT. OBJECTIVES

After you have worked through this unit, you will be able to:

1. Define Oxidation/Reduction using different definitions

2. Give examples of reducing agents and oxidizing agents

3. State the processes in the soil that undergo reduction/oxidation

4. Discuss oxidation of plant residues

5. Define Ammonification and nitrification

6. Describe redox reactions involving iron ions

7.1 OXIDATION/REDUCTION (REDOX) REACTIONS

Definitions

Oxidation and reduction in terms of electron transfer.

The definition of oxidation and reduction in terms of electron gain and loss is a more useful than the
first definition where oxygen is added or hydrogen is added to a substance. this is so because not all
reactions involve the addition or removal of hydrogen or oxygen.

Take for instance the reaction of chloride and iron chloride

2FeCl2 (aq) + Cl2 (g) 2FeCl2 (aq)
The equation in ionic form can be written as;

2Fe2+ (aq) + 2Cl- (aq) + Cl2 (g) 2Fe3+(aq) + 2Cl-(aq) + 2Cl-

43
 o The compounds in aqueous (solution) form are written in ionic form
o The molecules e.g. Cl2 which are non aqueous remain the way they are in the original
equation.

Writing the equations as half reactions;

The iron (ii) ions are losing electrons. This can be observed from balancing of the positive and
negative charge.
Fe2+ +- e- Fe3+
Charge Balancing
On the left side of the equation, we have, One negative from loss of e‐, the
+2 + (- x -) other from charge of electron (‐ve).
=+3
Negative multiplied by negative = positive

On the right hand side, the charge = +3.

So the equation is balanced.

This can be written as;

Fe2+ (aq) Fe3+ + e- Right hand side
Electron loss on the left hand side (+3-1) = +2 is the same as electron gain on the right hand side. In
the above reaction there are two processes taking place;
 Iron (ii) ions are losing to form Iron (iii)
Fe2+ (aq) Fe3+ + e-
The iron (ii) ions have been oxidized (loss of electrons)
 Chlorine atoms are gaining electrons from chloride ions
Cl2 (g) + 2e- 2C (g)
The chlorine gas has been reduced -gain of electrons (+2 electrons)

The above half equations are useful when considering oxidation and reduction.

Oxidation: - removal of electrons from an atom or a molecule.

Sn2+ - 2e- Sn4+

From +2 to +4

Fe – 3e- Fe3+ change of oxidation state: from 0 to +3

Reduction: addition of electrons to an atom or a molecule.

Fe3+ e- Fe2+

Or a decrease in oxidation state.

O2 + 4e- 2O2- Change in oxidation state: from 0 to -2 in the reaction:

Sn2+ + Fe3+ Fe2+ + Sn4+

Fe3+ ions are oxidizing agents and Sn2+ ions are reducing agents they reduce the Fe3+ ions to Fe2+

Other definitions

44
(i) Oxidation: reactions in which oxygen is added to, or hydrogen removed from a substance.

Example of oxidizing agents are:- nitric acid, sulphuric acid, potassium permanganate.

(ii) Reduction: reactions in which oxygen is removed from, or hydrogen added to a substance.

Nitrification and denitification are examples of oxidative and reductive reactions, respectively

8.2.1 OTHER REDOX REACTIONS

(i) REDOX REACTIONS INVOLVING IRON IONS:

Under aerobic conditions; the oxidization reactions:-

Fe2+ Fe3+ + e-

Is favoured and since the ferric ion is red, well aerated soils tend to be red or reddish – brown:
depending on the organic matter content of the soil. However under anaerobic conditions in poorly
drained soils, soil microbes use ferric ions for respiration, instead of O2 as terminal electron acceptors:

Fe3+ + e- Fe2+ giving a bluish – grey ferrous ions.

Consequently, water logged soils tend to be grey whereas intermittently water logged soils are
mottled grey and red. Microbial decomposition of humic substances leads to formation of sulphur
compounds such as H2S and mecarptans, which produce smell of rotten egg. (HCI). Strong oxidizing
agents such as HNO3 are therefore kept out of contact with metals.

UNIT SUMMARY

In this unit, you have been introduced to different definitions of reduction/oxidation. Examples of
reducing and oxidizing agents have been introduced to you. You have looked at oxidation/reduction
process of the soil. You have defined Ammonification and nitrification. In addition you described
redox reaction involving metals such as iron, copper and zinc. You have also been introduced to
important bacteria such as thiobacullus trioxides which help to catalyse the oxidation.

45
8. O INTRODUCTION TO ORGANIC CHEMISTRY

Organic chemistry

This unit deals with different concepts in organic chemistry. You will look at the branch of chemistry
which deals with carbon and compounds that carbon forms. All organic compounds contain carbon
atoms. However, not all carbon-containing compounds are classified as organic. There are a few
exceptions such as sodium carbonate, carbon monoxide and carbon dioxide that are considered
inorganic. Organic compounds then can be defined as covalently bonded compounds containing
carbon, excluding carbonates and oxides.

Unit Objectives
When you have gone through this module successfully you should be able to:
 Discuss key concepts in organic chemistry such as types of formula, and functional groups
 Define characteristics of organic reactions, types of reagents, mechanisms and types of
reactions
 State the physical properties of organic compounds

46
INTRODUCTION

Welcome to unit 1 Basic concepts in organic chemistry. This unit will introduce you to basic concepts
in organic chemistry. It is divided into 3 topics. The first topic discusses key concepts such as types of
formula and function group. The second topic will introduce you to characteristics or organic
reactions, types of reagents and types of reactions.

Unit session activities are placed at relevant segments. These should be completed before you
proceed to the next topic. The activities serve as an important input in understanding of later
materials.

Upon completion of this unit you will be able to

 Explain key concepts in organic chemistry

 Define characteristics of organic reactions, types of reagents and types of reactions
 Describe environmental concerns due to organic reactions

During the course of study you will come across a number of terms frequently used in organic
chemistry.

8.1 BASIC CONCEPTS

In this unit you will be introduced to common concepts used. Some of the concepts you will have
come across in first part of the course.. You will start by looking at what is meant by term:
Organic Chemistry – the study of covalently bonded carbon compounds though ionic bonds occur in a
few organic substances eg organic salts.
Reasons for studying carbon compounds separately from those of the other elements on the periodic
table are:
There are more compounds of carbon than of all other elements put together. There are more than 3
million known organic compounds compared to 60,000 inorganic compounds. With improved
technology, more and more organic compounds are being discovered. More are still being discovered
with the improving technology like in the field of medicine or agriculture.

All living organisms are made up principally of organic substances, and use a vast array of carbon
compounds in their growth and physiology. Carbon forms more compounds than any other element
due to a unique combination of three atomic properties:-

2.0.0 UNIQUENESS OF CARBON

Carbon is tetravalent in structure. It is always surrounded by four bonds when bonding

8.I Property A

Carbon has a high valence of 4 (tetravalent). To obtain a stable octet, each atom can share a pair of
electrons with four other atoms, including the carbon itself, giving single bonds.

47
 Eg ethane H H
H C C H (C2H6)
H H
If carbon bonds with a number of different atoms, its high valence alone can result in a large number
of possible compounds.

8.1.2 Property B

The single covalent bonds linking carbon atoms form chains of carbon atoms, both straight and
branched and of unlimited length, as well as the formation of rings of carbon atoms.

Eg Benzene C6H6 ringed molecules or Naphthaline (C10H8)

This linking of carbon atoms into chains and rings of different sizes and shapes makes it possible to
produce an enormous number of compounds of carbon.

8.1.3Property C

Formation of carbon to carbon double and triple bonds results in a further increase in the variety
organic compounds.
Eg Ethane C2H6 Ethene C2H4
H H H–C=C–H

H–C–C–H H H

H H

Straight or ringed or branched chains compound cancan be formed through the carbon bonding
Types of formula

Most of the formulas encountered in inorganic compound are the same as those in organic chemistry.

Using ethanoic acid as an example the following terms will be explained to you.

The empirical formula is CH2O which is defined as simplest formula showing the ratio in which atoms
are attached.

The molecular formula is C2H4O2 and it shows you the actual number of atoms of each element in
compound.

The structure formula is CH3COOH, and it gives you minimal detail in terms of how atoms exist in the
compound.

The displayed formula gives more information on how atoms are joined in the compound
You can now look at the functional groups commonly found in Organic Chemistry
CHARACTERISTICS OF ORGANIC REACTIONS.

There are several reactions that you will encounter in organic that are unique, one such reaction is
bond fission

There are two types of bond fission that you need to learn.

48
 1. hemolytic fission (free radical formation)
2. Heterolytic fission.

Hemolytic fission

This is an organic reaction which involves the breaking of a covalent bond followed by the formation
of new bonds.

For example compound AB

A: B A. + B.
Free reaction

The species formed have one electron each.

Heterolytic fission

Similar to the Hemolytic fission above the convalent bond breaking is followed by two species of
different (hetero) type

A: B A: - + B+

A: B A+ + B:-

Here you notice that there are two ions being formed, that is the positive and negative ion.

TYPES OF REAGENTS

You will also find peculiar reagents in organic chemistry.

(1) Free radical

From Hemolytic fission two reagents or species are formed of the same type.

 These species have impaired electron usually with single atoms, highly reactive and
often involved in chain reactions.
 They react by pairing of unpaired electrons

For example: Cl. + CH3. CH3Cl

Heterolytic fission will form an electrophile and nucleophile as products of bond breaking

(A) Electrophile

 This is the species which carries a positive charge – this implies that it is electron
deficient
 It attacks a carbon atom that is electron rich by accepting a pair of electrons.
.
Examples Br2 HBr, H2SO4 and Nitronium ion NO2+

49
 (B) Nucleophile

 This is an electron – rich species with a lone pair of electrons.

 It attacks a carbon atom that is electron - deficient by donating a pair of electrons.

Examples are :OH-, :Cl-, :NH3 H2O: and :CN

TYPES OF REACTIONS

The reactions you learnt in inorganic chemistry also apply in organic chemistry, although they might
slightly differ. The main types of reactions you will encounter are.

(1) Substitution

This is the swapping over the one species for another.

Substitution of Br- for OH- will be

CH3Br + OH- CH3 - Br- + OH-

(2) Addition reaction.

This is in which the addition of two species make one compound.

Unsaturated compound forming saturated
(3) Elimination reaction.
This is the opposite of addition. In this reaction you will find one compound breaking into two
compounds. You will notice that a saturated compound will form unsaturated compound.

e.g elimination of H2O from C2H5O.

H H H H
I I
H - C - C - OH C=C + H2O
I I
H H H H

Saturated unsaturated

(4) Hydrolysis reaction

This is a reaction where water breaks a bond. Example given

CH2COOCH5 + H2O CH3 COOH + CH3OH

(5) Oxidation reaction

This is a Gain of oxygen or loss of hydrogen (accompanied by loss of electrons to the organic
compound) e.g. hydrolysis of
50
C2H5OH + { O } CH3CHO + H2O

Reduction reaction

This is the loss of oxygen or gain of hydrogen (accompanied by the gain of electrons to the organic
compound)

An example reduction of CH3CHO

CH3CHO + 2{H} C2H5OH

Physical properties of organic compounds

Organic bonds are covalent bonded in nature, but you will find that some compounds exhibit some
polarity due to inductive effect.

Inductive effect
The inductive effect is a result from a difference in electro negativity which you came across inorganic
chemistry. This gives a polar molecule.

H Chlorine is more electronegative than

I carbon hence it pulls electrons near it
H - C + Cl  - there by producing a dipole.
I
H

Typical properties of polar organic compound are:-

 They have higher than expected boiling point and melting point. For example Alcohol.
 They are soluble in water (although) this decreases rapidly with increasing chain length you
will find that short chain alcohols dissolve in water but solubility decreases as chain
lengthens.

and
 and  bonds are molecular orbitals that bond together the atoms in a molecule.
Electron flow from carbon to chlorine – produces a dipole.

 In saturated compounds, you find all convalent compounds are  bonds.

 In unsaturated compounds there is one double bond in the chain and it is made up of both a
 - and  - bond.

 - bond

They are covalent bonds between C and H as well as bonds between C and C along the C – C chain
axis.

51
They are formed by the overlap of S and P atomic orbitals.

 bonds
 These are extra covalent bond in a double bond (C=C and C=O)
 They are above and below the c – c axis.
 They are formed by the overlap of the atomic p – orbitals

Non-polar compound.

This situation where atoms of similar electro negativity form a bond for example C and H means
Hydrocarbons are non-polar and dissolve in polar solvent, insoluble in water which is polar.

Polar compounds

Organic compounds molecules containing electronegative atoms of O, N or a halogen are polar.

For example:

Alcohols, carboxylic acids and amines contain OH or NH grounds. They are sufficiently polar to form
hydrogen bonds similar to those you dealt with when you learnt about water.

H H Oxygen more electronegative

Than hydrogen dipole produce
H C C O8-
H8+
H H

ACTIVITY 4 (15 minutes)

1. Mention two types of bond fission and give examples.
2. Describe the properties of
a) Free radical
b) Nucleophile

3. Define the following terms

a) Hydrolysis
b) Reduction
c) Inductive effect

52
8.1.4 Classification of Organic Compounds
Organic Compounds

Alicyclic or aliphatic Cyclic or closed chain

Or open chain compounds or ring compounds

Straight chain Branched chain Homocyclic or carbocyclic Heterocyclic

Aliphatic compounds compounds compounds
e.g n – butane e.g. isobutene e.g. pyridine

Alicyclic compounds Aromatic compound

Benzene e.g. cyclohexane

CH
HC CH Benzenoid aromatic Non - benzenoid

HC CH compounds aromatic compounds

CH e.g. benzene e.g. azulene

HC CH CH CH

HC CH HC CH CH C CH3

O HC CH CH CH
Furan N
Pyridine CH
Toluene
8.2.0 HOMOLOGOUS SERIES
All compounds having the same functional group or general formula whereby each molecule differs
from the succeeding or preceding one by a – CH2 – group and as a consequence, similarity in
methods of preparation, chemical properties, and reactions, constitute one class of compounds
known as a homologous series.

The physical properties of the homologous series show a regular gradation with increase in molecular
weight i.e. the Melting Point and the Boiling Point increase with increasing molecular weight within the
series.

53
The names of homologous series depend on the functional group of the series, the structures and the
names of the groups.

Definition:- Functional Group - a heteroatom or a group of atoms having at least one heteroatom
(atoms other than C and H) which determines the chemical characteristics of the given compound eg
N, O, S, Cl, P. These are atoms of a compound other than carbon and hydrogen only.

e.g - OH (Alcohols)
OH
- C = O (Carboxylic acids)
- NH2 (Amines) Or -N–H
H
- C = O (Aldehydes)
4.0.1 Some Examples of Functional Groups
Atom or Groups of atoms Name Class of compounds
- OH Hydroxyl Alcohols or alkanols
H
R-C=O Formyl Aldehydes or alkanals
R–C =O Carbonyl Ketones or alkanones
R’
OH
-C=O Carboxy Carboxylic acids
or alkanoic acids
- C - OOR Ester Esters
- NH2 Amino Amines
-C=O Amide Acid amides or amides
NH2
The properties of alcohols depend mainly on the hydroxyl functional group.
The properties of alcohols or fatty acids can be generalized by considering few representative
members of the series.

The length and branching of the hydrocarbon chain may have only a small effect on the chemistry of
the molecule, but will have a large effect on the physical properties especially the boiling and freezing
points, and their solubility in water; the water solubility.

Functional groups.

These are special atoms or group of atoms attached to a carbon chain. For example

Aliphatic compounds which are sometimes called straight chain hydrocarbons have a functional
group attached to a comparatively un-reactive carbon chain called an alkyl group.

H H H where x is function groups

I I I
H - C - C - C- x Functional group
I I I
54
 H H H
Alkyl Group

 The alkyl group has the composition CnH2n+1 (where n is the number of carbons in the chain)
 In organic chemistry you denote alkyl group using the letter R.
 Note that Alkyl groups are derived from alkanes.

The table 1 below shows some of the common alkyl groups.

Table 1 common alkyl groups

Number of carbon Alkane Alkyl group

1 CH4 Methane CH3- Methyl

2 C2H6 Ethane C2H5- Ethyl
3 C3H8 Propane C3H7- Propyl
4 C4H10 Butane C4H9- Butyl
5 C5H12 Pentane C5H11- Pentyl
6 C6H14 Hexane C6H13 hexyl

RULES FOR IUPAC NOMENCLATURE

The International Union of Pure and Applied Chemistry has found a set of rules for various types of
organic compounds. The guiding principle to be followed in writing the names of organic compounds
is that of substitution on a parent name. All such names are therefore also known as substitutive
names.

General Rules

1) It is considered that organic compounds derivatives of alkanes (or saturated hydrocarbons) are
formed by the suitable replacement the hydrogen(s) of the hydrocarbon(s) by various groups of
substituents. The naming of any organic compounds therefore depends on the correct selection of the
parent hydrocarbon chain of the basic carbon skeleton.

2) Select the longest possible continuous chain of carbon atoms which is called the parent chain. The
parent hydrocarbon is determined on the basis of the number of carbon atoms in the parent chain.
Others attached to it are referred to as side chains.

C–C–C–C–C The longest carbon chain contains five carbon atoms (pentane)
C
C
C– C–C–C–C
C– C C–C–C
The straight chain only contains five carbon atoms. The longest chain contains eight carbon atoms
(octane).
55
In case of two carbon chains with the same number of carbon atoms in the molecule,
the one which carries the larger number of side chains is selected as the parent chain.

C–C–C–C–C– C–C C C
C–C–C C C–C–C–C–C–C–C–C
3) The carbon atoms of the longest chain are then numbered by Arabic numerals 1, 2, 3, 4,
…………etc from one end to the other in such a manner that the carbon atoms carrying substituents
get the lowest numbers (lowest sum rule). The position of the side chains or substituents are indicated
by the number assigned to the carbon atom to which it is attached. The lowest sum rule can be used
if there are more than two substituents. The number that locates the position of the substituent is
known as a LOCANT.
C C C
C– C–C–C–C–C–C–C–C
4) The name of the substituent is prefixed, preceded by a locant to the name of the parent
hydrocarbon. A hyphen separates the locant from the name of the substituent

CH3 – CH2 – CH – CH3

CH3
5) If there are more than one substituents, each substituent is prefixed by its locant, placed in
alphabetical order preceding the name of the parent hydrocarbon. In case the same substituent is
present two, three or four times then the prefix di, tri, tetra is attached to the substituent’s name. Its
locates are written in the increasing order separated by commas amongst themselves and by a
hyphen from the substituent name.

eg CH3 CH3
.CH3 – CH – CH2 – CH – CH3 CH3
2, 4 – Dimethyl pentane CH3 CH2
H3C – CH – CH2 – CH – CH2 – CH2 – CH3
4 – Ethyl – 2 – methyl heptane

If the substituent on the parent chain has itself branched chain then it is named as a substituent alkyl
group and its carbon atoms are numbered from the carbon attached to parent chain. Such
substituent, indicating the position of the branched substituents on it, is written in parenthesis and
prefixed before the name of the parent hydrocarbon.

CH3 – CH2 –CH2 – CH2 – CH – CH2 – CH2 – CH2 – CH2 – CH3

CH2
CH3 – C – CH3
CH3 5 – (2, 2 – Dimethyl) propyl decane
6.0.2. NOMENCLATURE OF ALKANES
Three systems are generally adopted:-
6.0.3. (i) The Common System
In this system the first four members of the series are known as
 Methane (CH4)
 Ethane (C2H6)
 Propane (C3H8)
 Butane (C4H10)
Other members are named by prefixing Greek numeral, indicating the number
of carbon atoms in the molecule, to the suffix ‘ane’.

56
Molecular Formula Name
C5H12 Pentane
C6H14 Hexane
C7H16 Heptane
C8H18 Octane
C9H20 Nonane
C10H22 Decane
C11H24 Undecane
C12H26 Dodecane
C20H42 Eicosane
C40H82 Tetracontane
C80H162 Octantane

Some Examples of Radicals

General Formula of Radicals: CnH2n+1 -

Alkane Radical (Alkyl group) Formula (CnH2n+1 - )

Methane methyl CH3 –
Ethane ethyl C2H5 –
Propane propyl C3H7 –
Butane butyl C4H9 –
Pentane pentyl C5H11 –
Hexane hexyl C6H13 –
Heptane heptyl C7H15 –
Decane decyl C10H21 –

The ending ‘ane’ of alkane is replaced by ‘yl’ in radicals (the alkyl groups).

The saturated hydrocarbons usually have four types of carbon atoms in their molecules.

(i) Primary (1o) Carbon – A carbon atom having either one or none of its valences satisfied with
another carbon atom.

e.g C or C–C–

(ii) Secondary (2o) carbon – two valences of the carbon atom are satisfied with two other carbon
atoms.

e.g. C–C–C–

The primary and secondary hydrocarbons are also termed as ‘normal’ or n hydrocarbons. e.g.
n – pentane (normal pentane). They have a continuous or straight chain of carbon atoms.

(iii) Tertiary (3o) carbon – three valences of carbon atom are satisfied with three other carbon atoms.

e.g. C–C–C–
These are termed as ‘iso’ hydrocarbons.
C e.g. iso – pentane

(iv) Quaternary (4o) carbon – four valences of the carbon atom satisfied with four other carbon atoms.
e.g C
57
 C– C–C
C
These are termed as ‘neo’ hydrocarbons e.g. neo – pentane
6.0.4. (ii) As Derivatives of Methane
Higher paraffins are considered as derivatives of methane obtained by the replacement of its
hydrogen(s) by various alkyl groups(s).
e.g. Ethane Methyl methane H3C – CH3

Propane Dimethyl methane H3C – CH2 – CH3

n – butane Ethylmethyl methane CH3 – CH2 – CH2 – CH3

Iso – butane Trimethylmethane CH3

H3C –CH – CH3

Neo – pentane Tetramethylmethane

CH3
H3C – C – CH3
CH3
The highly branched carbon atoms of the paraffin is chosen as the methane carbon and the names of
alkyl radical attached to it are prefixed to the word methane in alphabetical order as one word.

8.2.10 (iii) The IUPAC System:-

The IUPAC system for paraffins is alkanes. In this system the common names of paraffins have been
retained for the straight chain hydrocarbons. The branched chain hydrocarbons are named by
selecting the longest continuous chain of carbon atoms as the parent chain. This chain of carbon
atoms is then numbered from one end to another by Arabic numerals so that various carbon atoms
having side chains get the lowest numbers (lowest sum rule).

8.2.2 Physical Properties of Alkanes

(i) The first four alkanes (C1 to C4) are colorless gases.
From pentane to heptadecane (C5 to C17) they are colorless ordourless liquids.
Higher alkanes are solids.

(ii) The alkanes are non-polar molecules about almost insoluble in polar solvents (water –
hydrophobic) but soluble in organic solvents (non – polar solvents) e.g. benzene, ether, carbon
tetrachloride. Solubility decreases with increasing molecular mass.

(iii) Physical constants like boiling point , melting point, density increase with increase in number of
carbon atoms..

(iv) The boiling point of alkanes having branched chain structure is lower than its isomeric straight
chain alkane.

(v) Alkanes with even number of carbon atoms have higher melting point than the one having odd
number of carbon atoms.
58
 C C C C C C
C C C C C C C

7.0.0. SUBSTITUTION REACTIONS

Alkanes are saturated in nature and therefore are inert but can undergo substitution reactions.
Because of their saturated nature they are comparatively stable to such usual chemical reagents as
potassium permanganate, potassium dichromate, chromic acid, nitric acid, sulphuric acid, sodium
hydroxide. The inertness of alkanes is the reason why they are known as paraffins (Latin, parum – a
little; affinis – affinity). They react with chlorine and bromine in the presence of sunlight and U.V. light
or at high temperatures resulting in successive replacement (substitution) of hydrogen atoms with
halogens (halogenation).
Extent of halogenation depends on the mole of halogen used.

U.V. light
(i) CH4 + Cl2 HCl + CH3Cl
Chloromethane (Methyl chloride)
U.V.light
(ii) CH3Cl + Cl2 HCl + CH2Cl2
Methylene dichloride
(Methylene chloride)
U.V. light
(iii) CH2Cl2 + Cl2 HCl + CHCl3
Chloroform (Trichlomethane)

UV light
(iv) CHCl3 + Cl2 HCl + CCl4
Carbon tetrachloride
or (Tetrachloro methane)

These replacement reactions where one or more hydrogen atoms are replaced by a halogen are
known substitution reactions. With fluorine, the reaction is too violent and with iodine the reaction is
too slow. The replacement of hydrogen atoms in simple alkanes by halogen atoms gives rise to a
number of useful compounds.

Compound Formula Use

Chloroform CHCl3 Anaesthetic
Carbon Tetrachloride CCl4 Dry cleaning solvent
- BHC (Hexachloro – hexane) C6H6Cl6 Organo chlorine insecticide
Methyl bromide CH3Br In soil sterilization
Iodoform CHI3 Antiseptic and local anaesthetic
Ethyl chloride C2H5Cl Local anaesthetic

Halogenated alkanes, like alkanes, are resistant to chemical attack. They therefore tend to
accumulate in the environment and in fat store in living tissues e.g. – BHC.

7.1.0 Some Uses of Paraffins

Natural or Bottled Gas – for household, laboratory and industrial heating; contains C1 to C4
alkanes.
Gasoline or Petrol – for internal combustion engines (contains C6 to C9 alkanes)
59
 Kerosine or Paraffin – for jet engines and heating; contains C10 to C16 alkanes
The complete combustion of an alkane is a highly exergonic reaction in the presence of adequate
oxygen. Alkanes are useful fuels for heating, lighting (household use) and fuelling engines.

e.g. combustion of methane

CH4 + 2O2 CO2 + 2H2O
(The reaction releases 8.9 x 105 J/mol of methane (213 Kcal/mole of methane). This is the amount of
heat energy released per mole of methane.

ORGANIC CHEMISTRY WORKSHEET I

(TUTORAL QUESTIONS) ATTEMPT ALL QUESTIONS
1) Write the structural formulas for the following
a) 2 – methyl pentane
b) 2, 3 – dimethyl butane
c) 2, 2 – dimethyl butane
d) 2, 2, 3 – trimethylhexane
e) 2, 3, 3 – trimethyl heptane
2) Name the following compounds

a) (CH3)2HCH(CH3)CH2C(CH3)3
b) CH3CH(CH3)C(CH3)2CH(CH3)CH3
c) (CH3)3CCH(CH3)2
(3) Write structures for the following compounds with the given formulas
Name each compound using the IUPAC System
C4H10
C5 H12
(4) Write the projection structures for each of the following compounds.
Name each compound using the IUPAC system
i) CH2(CH3)CH(CH3)CH3
ii) C(CH3)3C(CH3)2CH(C2H5)CH2CH3
iii) C(CH3)3C(CH3)2CH3
iv) CH3C(CH3)2CH(CH3)CH(C2H5)
v) C(C2H5)2(CH3)C(C2H5)2CH(CH3)2
5) a) Explain what you understand by the term ‘substitution reaction’
b) Write an equation for each of the following reactions and name the product of each reaction, using
one mole of ethane.
(i) 1 mole of chlorine (Cl2)
(ii) 2 moles of fluorine (F2)
(iii) 3 moles of bromine (Br2)
Name the products of each reaction.
6) Name the following compounds using the IUPAC system.
H2C CH2 ii) H2C CH2 iii) H2C CH2
H2C CH2 CH2 H2C CH2
H2C
iv) v)
HC CH3 H3C HC CH2
H2C CH2 H2C CH2
H2C CH2
H3C CH2
vi) vii)
H3C CH CH CH3 CH2 CH2
60
H3C CH CH2 CH2 CH CH3
CH CH3
viii) H3C HC CH CH3
H3C HC CH CH3
8.0.0. UNSATURATED HYDROCARBONS
These are divided into two groups:-

i) The alkenes or olefins which contain at least one carbon – carbon double bond

ii) Alkynes or acetylenes with one or more triple bonds

Unsaturation: one bond or more is available to bond with other atoms or H. Canstill add more atoms
or radicals.

8.0.1 ALKENES (OLEFINS)

- They are known as olefins because they form oily compounds with halogens.
General formula: CnH2n
For n =1, it does not exist

n=2 CH2 = CH2 or H–C=C–H (Ethane)

H H

NOMENCLATURE

The ending ‘ane’ of an alkane is replaced by ‘ene’ in alkenes

Alkane alkene
n=3 propane propene
n=4 butane butene
n=5 pentane pentene
n=6 hexane hexane

 With two double bonds in one molecule ending ‘ane’ of an alkane is replaced by ‘diene’
 With three double bonds, it is replaced by ‘triene’
 With four double bonds, it is replaced by ‘tetraene’
 With so many double bonds in one molecular structure the ‘ane” of alkane is replaced by
‘polyene’

Eg H H H H
H– C = C– C = C–H
Buta – 1, 3 – diene or 1, 3 – butadiene (meaning after the first carbon atom there
is a double bond also after the third one)
The double bond is located after the first and the third carbon atoms.

In the presence of a branched chain;

Draw structures of the following compounds

(i) 2 – methyl – 1 – butene
(ii) 2,3 – dimethyl – 1 - pentene
61
 (iv) 4,4,5 – trimethyl – 1,2 – hexadiene
(v) 1,2,3 – butatriene
(vi) Cyclo – 1,3 – butadiene or cyclobuta – 1,3 – diene

9.0.0 ISOMERISM
Definition:- Isomerism: the existence of organic compounds with similar and same number of atoms
but different arrangement of atoms. An isomer has the same number and type of atoms but these
atoms are arranged differently in the projection molecular structures.

An example- Position isomerism in butene molecules (C4H8)

Eg 1 – butene or (but – 1 – ene) and 2 – butene (or but – 2 – ene)

Examples of Some Types of Isomerism:-

 Position isomerism
 Functional isomerism
 Chain isomerism
 Geometric isomerism
 Ring – chain isomerism
 Stereo isomerism
 Optical isomerism

The more the number of carbon atoms in the molecular structure, the larger the number of isomers
obtained from the formula.

Q Give some few examples of isomeric compounds (structures) from the molecular formula
C4H10. and give name to each compound.

Methods of Preparation of Alkenes

Lower alkenes are prepared on large scale by cracking of petroleum and higher alkenes.
Some Few General Methods:-

Pyrolysis or Cracking: Higher alkanes when heated to a high temperature under pressure
decompose to give a mixture of alkanes and alkenes. The process that takes place in car engines
Definition: Cracking – the process of decomposition of less volatile higher hydrocarbons into more
volatile lower hydrocarbons with the application of heat and a catalyst.

9.1.2 General physical Characteristics of Alkenes

i) First three members of the alkene series are gases at room temperature. Alkenes having
five to fifteen carbon atoms – pentene to pentadecane (C5 to C15) are liquids. Higher
members are solids

ii) They are insoluble in water and soluble in certain organic solvents such as alcohols

iii) They have characteristic smell and burn with luminous flame (acetylene flame – in
welding)

iv) They are less volatile than alkanes.

62
General Chemical Characteristics of Alkenes

Alkenes are more reactive than alkanes due to the presence of the strained double bond in the
molecular structures of the alkenes.

Addition Reactions

a) Addition of hydrogen or hydrogenation:- Alkenes when heated with hydrogen gas in the
presence of catalysts eg Ni, temperature: 200 – 300oC, give alkane. The carbon – carbon double
bond is converted to carbon – carbon single bonds, the saturated compounds.

Equation:

RCH = CH2 + H2 RCH2CH3

Alkene alkane

CH2 = CH2 + H2 H3C – CH3

Ethene ethane

Application: In the margarine industry:- Raw materials for the manufacture of margarine are oils
(liquid lipids, eg groundnut, sunflower or cotton seed oil) which are made up of large molecules
containing long unsaturated hydrocarbons eg linoleic acid in diet of both human and animals. These
oils are hardened i.e. converted to more useful solid fats) by the saturation

b) Addition of halogens or halogenation

RCH = CH2 + X2 R – CH2CH2X

X
Alkenes react with halogens to form dihalogen derivatives (oily substances thus the name olefins) by
addition reaction.
Order of reactivity: Cl 2 > Br2 > I2

Test: Add drop wise bromine (Br2) dissolved in carbon tetrachloride to the substance under test. The
unsaturated compound will react with added bromine resulting in the disappearance of the
characteristic red – brown color of bromine.
In the food industry – It is applied in the quantitative estimation of the amount of unsaturation in the
liquid molecules.
This is normally expressed as ‘iodine number’ – defined as the mass of iodine absorbed (by
addition reactions) per 100g of sample of fat or oil.

e) Addition of Ozone (ozonolysis)

O
RCH = CH2 + O3 RC CH2 (ozonide)

O O

63
Ozone causes the rubber to perish by conversion of double bonds to single bonds in the process of
ozonolysis.

f) Addition of Paraffins (Alkylation) in the presence of HF, H2SO4, AlCl3

(CH3)2C = CH2 + HCH2CH(CH3) (CH3)3CCH2CH(CH3)2

2, 2, 4 – trimethyl pentane or iso –
octane

ACTIVITY 3

Give the IUPAC name for the following compounds.

(i)
H3C CH3

C = C

CH3 CH3

(ii) CH3

CH – CH2 - CH2 - CH3

CH3

(iii) CH3 CH2 CH3

I I
CH3 - C - CH2 - CH - CH - CH3
I I
CH3 CH3

(iv) CH3 CH - CH - CH = CH - CH = CH2

I
CH3

64
 (v) CH3 CH - C = C - CH2 - CH3

ACTIVITY 3 (20 minutes)

Write the structural formula

(i) 2,3 - dimethyl butane

(ii) 2 pentyne
(iii) 2 ethyl – 1 – butene
(iv) 1 , 5 – octadiene
(v) 2 ethyl 1 – 2 – methyl 1 – 1 – pentane

9.1 AROMATIC HYDROCARBONS

Two structures are used to represent benzene. The Morden delocalised being preferred.

Comparing arenes with alkene bonding.

Arenes and alkenes both have  bonds, but the electron density is less in arenas the greater stability
of arenes results from delocalised benzene ring compared with the localised electron density in
alkenes.

Types of reactions

Both alkenes and arenas react with electrophile. The typical reactions of arenes are substitution. The
benzene ring is represented.

i. addition reactions of benzene

Substitution reactions of benzene

Benzene undergoes a range of substitution reactions. These reactions are examples of electrophilic
substitutions. The delocalised benzene ring attracts electrophile.

Nitration of benzene
NO2
H2SO4
+ HNO3 + H2O
50oC
Mechanism

65
HNO3 + H2SO4 H2NO3+ + HSO-4
Loss of water molecule produces Nitronium ion

H2NO3 NO2+ + H2O

This is a powerful electrophile (NO2+) that reacts with benzene

NO+2 H NO2 NO2 + H+

Attack of electrophile

The H+ formed regenerates a H2SO4 molecule H+ + HSO-4 H2SO4 H2SO4 therefore acts as a
catalyst.

Halogenations of benzene for example chlorine of benzene

Cl

+ Cl2 Halogen carrier + HCl

e.g AlCl3
Reflux

Typically halogen carries are aluminium chlorine, AlCl3, or iron (iii) chlorine or Fe/Cl2 (Anhydrous
conditions)
Cl2 + A/Cl3 Cl+ + A/Cl- Cl+ this is a powerful electropile which reacts with benzene
Cl+ H Cl Cl

+ H+

Attack of Cl+ electrophile

The H+ formed regenerates an AlCl3 molecule

H+ + AlCl4- AlCl3 + HCl

A/Cl3 acts as a catalyst

Alkylation and acylation of benzene

Very important industrially similar principles and mechanism to chlorination (for example use of
Halogen carries).

RCl/halogen
66
 + HCl
Carrie

O
II
C R
RCOCl
Halogen carrie AlCl3 + HCl

Electrophilic substitutions reactions of methylbenzene

Methyl benzene is slightly more reactive than benzene.

The positive inductive effect of the methyl group increases the electron density of the benzene ring,
particularly at the 2, 4 and 6 positions.

Methyl benzene substitutes at the 2 – and 4 positions.

CH3 CH3 CH3

Cl2/A/Cl3(Anhydrous conditions Cl
+
Room Temp

Cl

CH3 CH3 CH3

HNO3/H2SO4 NO2

ACTIVITY 5

1. What is meant by unsaturated hydrocarbon?

2. Compare alkanes and arenes
3. Give an example of addition reaction of alkanes and one example of substitution reaction
of benzene

10.0. FUNCTIONAL GROUP ORGANIC CHEMISTRY

The hetero – atoms in the molecule is the functional group and will determine the chemical
characteristics of a particular homologous series.
Hetero - atoms:- atoms in the molecular structure other than carbon and hydrogen. E.g. I, O, S, P, N,
Cl, F

10.1 ALCOHOLS (ALKANOLS)

67
10.1.0. MONOHYDRIC ALCOHOLS

These are compounds considered to as hydroxyl derivatives of hydrocarbons obtained by replacing

one or more hydrogen atoms of a hydrocarbon (saturated or unsaturared0 by hydroxyl (- OH) group.
They are aliphatic (not aromatic) compounds containing one or more hydroxyl groups attached to
hydrocarbon chain which may be straight or branched, saturated or unsaturated.

Saturated monohydric alcohols constitute a homologous series having a general formula:-

CnH2n+1 – OH
And structured formula as R -.OH where R is an alkyl group.

Alcohols are further categorized as:-

i) Primary alcohols – The hydroxyl group in primary alcohols is linked to a primary (1o)
carbon.

Characteristic Group Type Formula Example Name

- CH2OH RCH2OH CH3CH2OH Ethanol
C2H5CH2OH Propanol

ii) Secondary alcohol: The – OH group is attached to a secondary (2o)

carbon atom.

Characteristic Group Type Formula Example

- CHOH R – CHOH CH3– CH – OH

CH3 (Isopropyl alcohol)

C2H5 – CH – OH

CH3 (2 – butanol)
Or (sec – butyl alcohol)

iii) Tertiary alcohol – the – OH group is attached to a tertiary (3o) carbon atom.

Characteristic Group Type formula Examples

R’ H3C

C – OH R C – OH H3C C – OH

R’’ H3C (Tert-butyl alcohol)

11.1 NOMENCLATURE

68
Three systems are used for naming the alcohols:-

Common system – simpler alcohols are named after the alkyl group to the hydroxyl group is attached.

e.g. CH3OH Methyl alcohol

C2H5OH Ethyl alcohol

IUPAC system: In this system, alcohols are named as alkanols and the name of a particular member
is obtained by replacing the ending ‘e’ of alkane (parent hydrocarbon) by suffix ‘ol’.
Alkane Alcohol
Ethane Ethanol
Butane Butanol

11.3.0 General Methods of Formation of Alcohols

Ethanol: - also known as grain alcohol.

Source: starch, grains products in plants by fermentation (decomposition).

It can be obtained from such sugars as sucrose, (cane sugar), glucose or from molasses.

C12H22O11 + H2O Invertase C6H12O6 + C6H12O6

(Yeast) glucose fructose

C6H12O6 Zymase C2H5OH + CO2

(Yeast)

Ethanol and butanol can be prepared by the following methods

(1) From Grignard reagents:- the Grignard reagents may be used for the preparation of all three
types of alcohols 1o, 2o and 3o alcohols.
Br
C2H5MgBr + ½O2 C2H5.O MgBr C2H5OH + Mg
Ethyl magnesium bromide Ethanol
OH
2) By Fermentation of Carbohydrates
Those prepared by this method are:-
 Ethanol
 Butanol

Compounds like carbohydrates (polyhydroxy carbonyl compounds decompose to yield alcohols in the
presence of suitable micro – organisms, which are the source of biochemical catalysts known as
enzymes.

C6H12O6 2C2H5OH + CO2

Glucose ethanol

n(C6H10O5) CH3CH2CH2CH2OH + CH3COCH3

Starch butanol acetone

Enzymes: B. marcernus
69
 B. chosdricum acetobutylicum

10.3. 1. MANUFACTURE OF ETHANOL BY FERMENTATION

This is done in stages:

(a). Saccharification

The starch is first converted to sugar by the following steps:-

i) Malting:- Germinated barley seeds known as malt contain an enzyme diastase which hydrolyses
the starch to maltose.

 Moist barley seeds are allowed to germinate in dark at 15oc

 When germination is complete the temperature is raised to 60oC to stop further growth
 The seeds are then crushed in water and filtered. This filtrate containing the enzyme diastase
is known as malt extract.

ii) Mashing:- the process of liberating starch materials. Substances like potatoes maize, barley are
crushed and then heated with superheated steam under pressure.

- The starch present in the material forms a paste with water known as mash.

iii) Hydrolysis of Starch:- Malt extract prepared in (i) is added to mash at a temperature of 50oC to
60oC. The enzyme diastase hydrolyses the starch to maltose in about half an hour.

(C6H10O5)n + H2O Diastase n(C6H22O11)

Starch Maltose

(b) Fermentation:- Hydrolyzed starch solution containing maltose (orgecose)is fermented by yeast for
2 – 3 days at 30oC. The enzyme maltose present in yeast hydrolyses maltose to glucose which is
converted to ethanol by another enzyme zymase.

C12H22O11 + H2O Maltase n C6H12O6 Zymase 2C2H5OH + H2O

Maltose Yeast Glucose Yeast Ethanol

The fermented solution contains approximately 10% ethanol and is known as wort. Fractional
distillation of wort gives rectified spirit in 90% alcohol.
Uses of Ethanol

One of the most extensively used organic compounds

a) As an alcohol
b) As a solvent for paints, drugs, oils, perfumes, dyes, varnishes gums
c) As a solvent for pharmaceutical preparations and a constitute of medication
d) As a preservative for biological specimens
e) As an antifreeze for automobile radiators
f) In scientific apparatus like spirit levels
70
 g) As a substitute for petrol (power alcohol)
h) As a fuel in spirit lamps and stoves
i) In the use of a large number of organic compounds like ether, acetaldehyde, chloroform,
iodoform, chloral, acetic acid.
j) As a reaction medium, extractant and a crystallizing medium.

10.4 Uses of Monohydric Alcohols

Methanol
Source: By destructive distillation of hardwood (wood alcohol) and condensing the vapor produced.
Methanol is highly toxic, causing blindness in humans, as well as insanity and death. It is extremely
poisonous.
It is used:
(i) As a solvent for oils, fats, paints and varnishes
(ii) As an antifreeze in automobile radiators
(iii) In the manufacture of dyes, drugs and perfumes
(iv) For denaturing ethyl alcohol (so that it is not consumed)
(v) As a petrol substitute

10.4. Uses of Higher Monohydric Alcohols

(i) Capryl alcohol or 2 – octanol (CH3(CH2)5CHOH(CH3)

- A secondary alcohol used as a substitute for butanol in the production of resins in the manufacture
of esters which are used as plasticizers, oil additives as antiforming agents.

(ii) Lauryl alcohol or dodecanol – 1 (C12H25OH)

- A primary alcohol used in the manufacture of sodium lauryl sulphonate used as a detergent

(iii) Cetyl alcohol or hexadecanol (C16H33OH)

- A primary alcohol
 Used in the manufacture of sodium cetyl sulphate; a detergent
 In cosmetic preparations
 As a softening agent for the textile fabrics

(iv) Stearyl alcohol or octadecanol (C18H37OH)

A primary alcohol used widely
 In the preparation of sodium stearyl sulphate – a detergent
 The ester from this alcohol used in the plasticizer
 In cosmetic manufacture.

10.4.2 DIHYDRIC AND TRIHYDRIC ALCOHOLS

(Diols and Triols)

Diols or Glycols – they contain two hydroxyl groups in their molecular structures and are known as
dihydric alcohols. Because of their sweet taste they are also known as glycols (Greek : glykys –
sweet)

Nomenclature
Formula Common Name IUPAC Name
71
CH2OHCH2OH Ethylene glycol Ethane – 1,2 – diol
CH3CHOHCH2OH Propylene glycol Propane – 1,2 – diol

Uses of Ethylene Glycol

 As an atifreeze in automobile radiators (trade name – prestonel)
 For preventing deposition and formation of ice on aeroplane wings
 In making low freezing dynamites
 As a coolant for aeroplane engines
 As a solvent and preservative
 As a plasticizer for viscose rayon and an intermediate in the manufacture of polyurethane
polymers
 In preparation of such compounds as dioxane, diethlyene glycol (used as a solvent), ethylene
dinitrate or nitroglycol (used as explosive) and glycol stearate (used as a lubricant for springs)
 As dielectric in electrical condensers
 In the manufacture of synthetic polyester fibre – terylene.

10.4.2. TRIOLS OR GLYCEROLS

Glycerol may be considered as a derivative of propane, obtained by the replacement of three
hydrogen atoms from different carbon atoms by three hydroxyl groups.

Occurrence: in combined state as glyceryl ester of higher fatty acids in almost all vegetable and
animal fats and oils. The higher fatty acids present in glyceryl esters are usually Palmitic acid
(C15H31COOH), Stearic acid (C18H37COOH) and oleic acid (C17H33COOH0 acid. Their esters with
glycerol are also known as known as glycerides.

Preparation:
Glycerol is prepared by the following methods. From fats and oils – when hydrolyzed fats and oils
yield fatty acids and glycerols. These fatty acids find use in the manufacture of candles or as soaps in
the form of sodium or potassium salts. The fats and oils are hydrolyzed either with alkali (in soap
industry – saponification) or by superheated steam (in candle industry and glycerol is obtained as a
byproduct).

CH2OOCC18H35 CH2OH

CHOOCC18H35 + 3KOH CHOH + 3C18H35COOKa

soap
CH2OOCC18H35 CH2OH
Stearin Glycerol

(b) From the sweet water of the candle industry.

In the manufacture of candles, higher fatty acids like stearic acid are mixed with other fatty acids.
These higher fatty acids are obtained from hydrolysis of fats and oils with superheated steam using
dilute sulphuric acid as a catalyst. These fatty acids are usually solids and are removed by filtration.
The filtrate is known as sweet water.
Constituents of sweet water are; water, glycerol, and free fatty acids.

10.4.3 Uses of Glycerol

(i) As a sweetening agent in confectionary, beverages and medicines
(ii) As a preservative
(iii) In the preparation of good quality soaps and cosmetics
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 (iv) As an antifreeze in automobile radiators
(v) As a lubricant in watches
(vi) As a moisture conditioner for tobacco products
(vii) In the preparation of non drying inks, printing inks and stamp pad inks
(viii) As a plasticizer of cellophane
(ix) In the preparation of various organic compounds like formic acid, alkyl alcohol,
acrolein
(x) In the manufacture of glycerol esters like glyceryl trinitrate (for nitroglycerine) used in
making dynamite, cordite and blasting gelatin.

10.4.4 Polyhydric Alcohols (Polyols)

Monosaccharides are polyhydroxy alcohols e.g. glucose

O OH H OH OH OH

H C C C C C C H

H OH H H H

Many other biochemical molecules contain the hydroxyl groups e.g. Vitamin A1 (Retinol)

10.5.0. CARBOXYLIC ACIDS (FATTY ACIDS)

Carboxylic acids contain both the carbonyl ( C = O) and the hydroxyl (-OH) groups attached to the
same carbon atom.

The – C – OH is the functional group

General Formula: CnH2n+1 – COOH for monocarboxylic acids.

Or R – COOH
O
Or R – C OH
The first member of the series is formic acid (HCOOH)
- From Latin word - formica meaning ant. It is obtained by the distillation of ants
Formic acid is also known as methanoic acid.
The ending ‘e,’ of an alkane is replaced by ‘oic’
Formic acid occurs in the sting of bees, wasps, red ants, fruits and also as a trace element in
perspiration, urine, blood and in caterpillars.
Uses;
 As an antiseptic and in preservation of fruits
 In tanning for removing lime from the hides
 In coagulating rubber latex
 In treatment of gout
 As a stimulant for growth of yeast

Second member of the series: Acetic acid (or ethanoic acid - CH3COOH)
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In free form it occurs in fruit juices which have undergone fermentation. It is a constituent of vinegar.
(Latin: acetum – vinegar).

Dicarboxylic Acids

They have two - COOH groups in their molecular structure

Examples of Dicarboxylic Acids

Formula Common Name IUPAC Name

(COOH)2 Oxalic acid Ethanedioic acid

(CH2)2(COOH)2 Succinic acid Butanedioic acid
(CH2)4(COOH)2 Adipic acid Hexane -1, 6 – dioic acid

Substituted Acids:
(i) Glycolic acid (hydroxyacetic acid) CH2OHCOOH - occurs in juice of sugarcane,
tomato, unripe grape and beet.
(ii) Lactic acid hydroxypropionic acid (CH3CHOHCOOH) – occurs in sour milk (L.
lactum – milk), gastric juice, cucumbers and opium.
(iii) Tartaric acid (Dihydroxy succinic acid ) It contains two asymmetric
carbon atoms

Tartaric acid molecule:

(2, 3 – dihydroxy – 1, 4 – butanedioic acid)
HCOH.COOH
HCOH.COOH
It exists in four stereo isomerism forms
 Laevo
 Dextro
 Meso
 Racenic
Structures
COOH COOH C – OOH
HO C H H C OH H C OH
H C OH HO C H H C OH
COOH COOH C – OOH
d – tartaric acid l – tartaric acid meso – tartaric acid
Naturally occurring d – tartaric acid is dextro – rotatory. It occurs in free state as potassium acid salt in
various fruits (e.g grapes, plums, barriers), also argol – a brown coloured mass formed during
fermentation of grape juice.

iv) Citric Acid: (3 – carboxy – 3 – hydroxypentan - 1, 5 – dioic acid)

It occurs in many fruits e.g tomato, orange, especially in unripe fruits of citrus group. eg lemon
Lemon juice contains 6 to 10% of citric acid.

ESTERS AND ESTERIFICATION

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Esters are substances obtained by the reaction between an alcohol with an acid, organic or inorganic.
The process of formation of an ester is known as ‘esterification’. It is a slow and reversible process
and usually takes place in the presence of a suitable dehydrating agent..

Esterification is analogous to salt formation i.e. neutralization, takes place by the reaction of an acid
and a base.

Acid + Base Salt + Water

Fatty acid + alcohol Ester + Water

General Formula: O

R – C – O – R’
Where R is H
or CnH2n+ 1
and R’ is CnH2n+1 for which both R and R’ are alkyl groups.
e.g. HCOOCH3 - methyl formate or methyl methanoate
Reactions;
Acid + Base Salt + Water
HCl + NaOH NaCl + H2O

Fatty acid + Alcohol Ester + Water

CH3COOH + CH3OH CH3COOCH3 + H2O
Acetic acid Methanol Methyl acetate water

The methyl formate (HCOOCH3) – is a liquid with B.P. of 31.8oC.

It is used as a fumigant and larvicide for cereals and tobacco.
Ethyl formate – a liquid with B.P. of 54.2oC
- used in the synthesis of vitamin B1
- as an ingredient for artificial rum
Many esters have pleasant smells which help in their identification. They can be hydrolysed back to
the original fatty acid and alcohol under alkaline conditions.

Esterification (low pH)

Alcohol + Fatty acid Ester + water
Hydrolysis (high pH)

10.5.1 Other Uses Of Esters:-

- They are important as flavourings, solvents, drugs, perfumes and as synthetic textiles
(e.g. polyester fibres) or plasticizers
They are used as special lubricants (long – chain esters).
Esters are responsible for the smell and flavour of many fruits and flowers. The artificial flavouring
essences are prepared from esters.

- In biochemistry there are two groups of highly important complex esters:-

 The triglycerides e.g. palmitin, an ester in the soap industry
 As high energy esters e.g. alkyl phosphates and thioesters

75
(i) - Esters are responsible for the smell and flavours of many fruits and flowers. The artificial
flavouring essences are prepared from esters. Ethyl methanoate is used in raspberry essence and 3 –
methylbutyl ethanoate in pear essence.

(ii) - Esters are also used in artificial scents (perfumes).

(iii) - Waxes are esters of higher carboxylic acids and higher alcohols.
e.g. a constituent of beeswax is C15H31COOC31H63

(iv) - Fats and oils are esters of higher carboxylic acids and propane – 1, 2, 3 – triol. These esters are
known as glycerides, and some are used in the manufacture of soaps.

SAPONIFICATION

- The hydrolysis of fats and oils by alkalis is known as saponification.

Equation:

CH2 – O – C – C15H31 CH2 – OH

O

CH – O – C – C15H31 + 3NaOH CH – OH + C15H31COONa

O Sodium palmitate
(a soap)
CH2 – O – C – C15H31 CH2 - OH
Palmitin (an ester - a glyceride) Glycerol (Trihydric alcohol)

Saponification Value:- is defined as the number of milligrams of potassium hydroxide required to

completely saponify 1gm of fat or oil.
Or the amount in mg of potassium hydroxide required to neutralise completely the fatty acids resulting
from complete hydrolysis of 1gm fat r oil.

The saponification value gives an idea about the molecular weight of fat or oil. The smaller the
saponification value the higher the molecular of the fat or oil
It is useful in:-
- Calculating the amount of alkali needed to for converting a definite amount of fat or
oil into soap
76
 - Detecting the adulteration of a fat or oil by one of lower or higher of saponification
value.

Acid value:- The number of milligrams of potassium hydroxide required to neutralize the free organic
acids present in 1gm of fat or oil.
The difference between saponification value and acid value is known as the ester value of the fat or
oil.

Synthetic Detergents (Syndets)

Surface active agents, other than soaps have been found to possess cleaning property.
These are called soapless detergents or soapless soaps or syndets. They are more resistant to hard
water than soaps. Syndets contain both hydrophilic (water soluble) and hydrophobic (oil soluble) part.

e.g. sodium lauryl sulphate sodium palmitate

C12H25 OSO3Na C16H33 COONa

Hydrophobic Hydrophilic part Hydrophobic part Hydrophilic part

Some Examples of Synthetic Detergents

(a) Sodium alkyl sulphates

(i) C12H25 – O – SO2 – ONa (sodium luaryl sulphate)
(ii) C16H33 – O – SO2 – ONa (Sodium cetyl sulphate
They do not produce hydroxyl ions on hydrolysis and so can be safely used for woollen garments.
They equally work well hard water and soft water.

(b) Quaternary ammonium salts

Br-
e.g. trimethyl stearyl ammonium bromide (CH3)3 N+

C18H35
(c) Partially esterified polyhydroxy compounds

e.g. CH2OH

C18H35COOCH2 – C – CH2 – OH

CH2OH

(d) Substituted alkyl sulphonates

e.g. Sodium – p – dodecyl – benzene – sulphonate

C12H25 O.SO2Na

Sulphonates with triethanol ammonium ion in place of sodium serve as highly soluble material for
liquid detergents
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 R O – SO2 C(CH3.CH2.OH)3NH+

Synthetic detergents or syndets may be

a) anionic surface active (e.g. sodium cetyl sulphate, dreft, sandopan)
b) cataionic surface active (e.g. cetyl trimethyl ammonium halides)
c) non – ionic surface active

10.5.3 Uses of Synthetic Detergents

- House hold cleansers. For textile bleaching

- Metal cleaning
- Cleaning and sterilizing food processing equipment
- In cosmetics
- In tanning and dyeing leather
- Ore floatation
- For fire fighting
- In emulsion polymerization of synthetic rubber
- As antibacterial
WORKSHEET III
TUTORIAL QUESTIONS (ATTEMPT ALL QUESTIONS)
1) Briefly explain what you understand by the following terms:-
a) Chain isomerism
b) Geometrical isomerism
c) Functional isomerism
d) Position isomerism
e) Ring chain isomerism
Give examples for each type of isomerism using the molecular formula C4H8 and name each
compound using the IUPAC system.

2) Complete the following chemical reactions:-

(i) CH3COOH + CH3OH

(ii) CH3CH2CH3 + 2I2
(iii) CH3CHCHCHCH2 + 2HBr
(iv) CH 4 + 4Cl2
(v) CH2CHCH3 + HBr
(vi) CH3CHCHCH3 + HCl
(vii) CH2CCCHCH2CH3 + HBr
(viii) CH2CCHCCH2CH3 + 2HI
(ix) CH2CHCHCH2 + 2HF
(x) CH2CHCHCHCHCH2 + 3HF

3) Explain the following reactions:-

(i) Cannizzaro’s reaction
(ii) Markovnikov’s rule
(iii) The formation of a Zwitter ion

4) What do you understand by the following as applied to fats and oils?

a) Drying of fat or oil
b) Adulteration of fat or oil

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5) Distinguish between ‘addition polymerization’ and ‘condensation polymerization’
Give one example of each polymer formed as a result of each of the above processes.

6) Explain what you understand by the following terms:-

a) Iodine number of fat or oil
b) Ester value of fat or oil
c) Acid value of fat or oil

7) (a) Outline some of the uses of synthetic detergents.

(b) Why are the synthetic detergents more efficient in the cleaning of materials than the ordinary
soaps?
10.6. SYNTHETIC DETERGENTS (SPREADERS -WETTERS AND CLEANSERS)
Detergents are amphipathic organic molecules with one end – having a hydrophilic functional group
And the other end – a long hydrophobic hydrocarbon chain more than 8 carbon atoms in the chain
O – SO3-
Hydrophobic end hydrophilic end
Synthetic detergents
 A sulphate ( - O – SO3-)
 A sulphonate ( - C6H4SO3-)
 Or phosphate group

Soaps have a carboxylate group

CO2-Na+

Soaps cannot be used in ‘hard water’. This is due to the precipitation of the Mg, Ca, and Fe salts

Equation: Ca2+ + 2CH3(CH2)16 Ca(CH3(CH2)16CO2)2 (scum)

Since syndets do not form precipitates in hard water they can be used for the cleansing purposes.

Spreaders in Chemical Spray

The surface of the leaf is hydrophobic implying that when the water is sprayed on the surface it forms
some droplets, not all the leaf surface is covered. This prevents the chemical from covering the whole
leaf surface during spraying.
When a spreader is mixed with the spray chemical, the spray droplets containing the detergent (or
spreader) are in contact with the leaf surface. The hydrophobic ‘tails’ of the detergent molecules are
attracted to the hydrophobic surface of the leaf. The hydrophilic ends remain in water

The high surface tension of water of water is overcome in the presence of the syndet. The spray
droplets adhere to and cover the whole leaf surface. When water evaporates the whole leaf surface is
covered by the chemical coming in contact with all the pests on the leaf surface.

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12.2.0 Detergent Action in Removing Dirt

When the synthetic detergent is introduced into the greasy/oily material, the tails of soap molecules
are attracted to the greasy material. The hydrophilic ends remain in water. When rubbing in soapy
water, particles of dirt are detached from the skin at the centre of the soluble misceles forming very
small droplets of greasy material. These can be removed from the linen. The dirt water has these
dispersed and can be removed in water as dirt.

CO2
CO2-- CO2-

CO2- CO2- CO2- CO2- CO2- CO2-

CO2- CO2-

CO2- CO2- CO2-

CO2-
CO2-
CO2- CO2-
CO2- CO2-
CO2- CO2-
Synthetic detergents can also be applied in the dispersion of oil in sea pollution. The oil is dispersed
forming droplets in water.

Wetting of Surface
If a droplet is placed on a hydrophilic surface, (e.g. glass, or cotton cloth or clay) which carry the
hydroxyl groups, the hydrogen bonds can form between the outermost molecules in the water droplet
and the hydroxyl groups on the hydrophilic surface. The – OH group of the surface bonds with the
hydrogen bond of water.
This neutralizes the inwardly directed forces and reduces the surface tension of the water. This
enables the droplet to spread thinly over the surface. The water droplet can wet, and adhere to the
surface.

The successful wetting of hydrophobic surfaces is an important problem in the application of

pesticides. In spraying the crop with insecticide or fungicide, it is necessary to cover the leaves
uniformly with spray so that when the water evaporates the active ingredients is uniformly distributed,
giving complete protection.

Inwardly directed forces creating the surface tension for the

liquid forming droplets

Reduced surface tension

OH OH OH OH OH

Water spreads on leaf surface

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The hair and hides of livestock tend to be greasy and hydrophobic, repelling aqueous dip solutions.
The synthetic detergents are applied to reduce the surface tension of the droplets or spread the
chemical

Definition: Surface Tension of a liquid is an index of the amount of work required togive unit increase
in the surface area of volume of liquid (measured under standard conditions)

The table below gives the surface tension of the selected liquids in contact with air at 20oC

Surface Tension in nN m-1

Water 72.75

Benzene 28.83

Acetic acid 27.60

Carbon tetrachloride 26.80

Ethanol 22.30

Mercury 485.00

The liquids with unusually strong intermolecular forces (e.g. water) or inter atomic forces (mercury)
have high surface tensions.

10.7.0.0 AMINES AND AMINO ACIDS

10.7.1 AMINES (AMMONIA DERIVATIVES)
These are derived from ammonia by the replacement of one or more hydrogen atoms in an ammonia
molecule by alkyl groups.
If only one hydrogen is replaced a 1o (primary amine) is obtained.

H H H
H–N–H H–C–N–H or CH3NH2
H (Methylamine)
C2H5NH2 C3H7NH2
H H H H H H H
H–C–C–N–H H–C–C–C–N–H
H H H H H
Ethylamine Propylamine
The general formula for amines is R – NH2 for primary amines
Or CnH2n+1 – NH2
Where – NH2 is the amino group and CnH2n+1 – or (R) is the alkyl group
H
R – N – H (primary amine)
(ii) Replacement of 2 hydrogen atoms in ammonia molecule by two alkyl groups forms a secondary
amine.
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 H3C – N – H H3C – N – H
CH3 C2H5
Dimethylamine Ethylmethylamine
The General Formula for the 2o Amines is:-
R–N–H
R’

The tertiary (3o) amines are formed by replacing all hydrogen atoms in ammonia by alkyl groups.

H3C – N – CH3 H3C – N – C3H7

CH3 CH3
Trimethylamine Dimethyl propylamine
General formula for tertiary amines is R – N – R’
R’’
NB - 1o amines contain the – NH2 group, the 2o amines have – N – H group and the tertiary amines
3o have – N – group.

The - NH2 group is known as the amino group and the – NH group is known as the imino group.

Some important Amines

a) Simple aliphatic amines – which account for strong smells of fish and fish products.
e.g. CH3NH2, (CH3)2NH, (CH3)3N, C2H5NH2
Tertiary amines occurring in bad silage – toxic to ruminants

b) Choline in muscle tissues or a quartenary ammonium compound, acetylcholine – a derivative

of choline – chemical transmitter of nerve impulses

CH3 O

H2C – N+– CH2 – CH2 – O – C – CH3

CH3

c) Synthetic diamine EDTA – (ethylene diamine tetraacetic acid)

-
a chelating agent widely used in the solution and chemical analysis of sparingly
soluble cations e.g. Ca2+

HOOCCH2 CH2COOH
N – CH2 – CH2 – N
HOOCCH2 CH2COOH

d) Naturally occurring amine bases known as alkaloids

a. Nicotine
b. Atropine (an antidote for organo phosphorus pesticide poisoning)
c. Quinine (for treatment of malaria)
d. Indol – 3yl – acetic acid (auxin – plant growth regulator)

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 e) Nucleic acids –– RNA, DNA with ribose molecule – phosphate group and a complex amine

Properties and Characteristics of Amines

 Lower members are combustible at ordinary temperature. C3 to C11 are volatile liquids. Higher
members are solids.
 Lower members have fishy ammoniacal odour, which vanishes in higher members.
 The lower members are soluble in water; solubility decreases with increase in molecular
weight.
 The boiling point increases with increase in molecular weight
 Aqueous solutions are alkaline to litmus and conduct electricity (ammonia solution)

Uses of Amines
(i) Inhibitors: Amines are effective at preventing the deterioration of rubber through
oxidation by atmospheric oxygen.
(ii) Plastics: 1, 6 – Diaminohexane, H2N – (CH2)6 – NH2, is used in the manufacture of
nylon – 6, 6. Other amines are used in the production of isocyanates for polyurethane
plastics.
(iii) Dye – stuffs: Primary aromatic amines are used to make azo – dyes.
(iv) Medicines: Amines are used in the manufacture of many pharmaceuticals (e.g.
Palludrine, an anti-malarial drug).

AMINO ACIDS:-
(a) - They are amino substituted acids containing both the amino (-NH2) and carboxyl (-COOH)
groups. One part of the molecule donates a proton whereas the other part receives the proton
(b) - Simple amino acids having only one amino group and one carboxyl group may be classified as
α, β, γ, δ amino acids depending on the position of the amino group with respect to carboxyl
group.

α- Amino acids

H2NCH2COOH Amino acetic acid (glycine)

CH3CH(NH2)COOH α - Amino propionic acid or 2 – amino propanoic acid
C6H5CH2(NH2)COOH α - Amino - phenylpropionic acid (phenyl alanine)

β - Amino acids

H2NCH2CH2COOH α - Amino propionic acid or 3 – amino propanoic acid

CH3CH(NH2)CH2COOH β- amino butyric acid or 3 – amino butanoic acid
γ- Amino acid

CH3NH2CHCH2CH2COOH γ- Amino butyric acid or 4 – amino pentanoic acid

Of these the α - amino acids are the most important because they are the final product of the
hydrolysis of peptides and proteins

Only about 100 amino acids have so far been obtained from natural sources; most of them are α -
amino acids. The 26 known amino acids can be combined in different forms to form a large variety of
proteins.

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Living organisms differ in their ability to synthesize amino acids that are necessary for proper growth
and maintenance of life. There are 8 such α - amino acids whose absence in human body may even
cause death but which the body cannot synthesize. They are known as essential or indispensable
amino acids because they are essential in the diet.

All α - amino acids except glycine, obtained from natural sources are optically active because of
asymmetric α - carbon atom. All α - amino acids obtained from animal or plant sources have l –
configuration at the α - carbon atom.

Examples of α – Amino acids Present in Proteins

1) Glycine
H2N – CH2 – COOH

2) α – Alanine

H2N – CH – COOH

CH3
3) Valine

H3C – CH – CH3

H3N – CH – COOH

4) Phenylaline

C6H5 – CH2 – CH – COOH

NH2
5) Cystene

HS – CH2 – CH – COOH

NH2

6) Lysine H2N – (CH2)4 – CH – COOH

NH2
Amino acids are the building blocks of proteins combined by condensation polymerisation in different
patterns. A water molecule is given off in the process.
The α – amino acids are the most important in the diet. They are the final products of hydrolysis of
peptides and proteins, From the 26 amino acids combinations yield a variety of proteins.

 Most amino acids isolated are α – amino acids

 From the 26 amino acids combinations yield a variety of proteins – combined in different
forms
 Synthesis of amino acids differs in living organisms
84
  The 8 α – amino acids are essential in the diet
 α -amino acids have l – configuration
 They have (except glycine) asymmetric carbon atoms

The Zwitter ion (Amphoteric Substances)

Amino acids behave as if they are neither basic nor acidic. They are dipolar ions or Zwitter ion
(German: Zwitter – hermaphrodite).
.
Amino acids can behave as acids (proton donors) or as bases (proton acceptors) under certain
conditions. Such substances which contribute to the pH – buffering of living tissues are called
Amphoteric
In solution the zwitter ion is in equilibrium with a little of the covalent form:

H2N+ – CHR – COO - H2N-CHR-COOH

Adding an acid to the solution, the zwitter ion in (a) is converted to the cation (b). The acid makes the
proton available to the carboxylate ion.

H3N+.CHR.COO - + H3O+ H3N+CHR.COOH + H2O

Adding the strong base to the amino acid, the zwitter ion in (a) is converted to the anion (c). The
strong base OH – takes away a proton from the ammonium ion forming an anion.

H3N+CHR.COO - + OH - H2N.CHR.COO - + H2O

So in the strong acid medium, the acids migrate towards the cathode in an electric field
In the presence of a strong base the amino acid migrates towards the anode. The structure of a
zwitter ion for an amino acid can be proven.

So at a particular pH the concentration of cation (b) can be exactly the same as the concentration of
the anion (c). Hence at this pH there is no migration of the amino acid in the electric field. At this pH at
which the amino acid does not migrate in an electric field this is known is the ‘iso – electric point.’ At
the iso - electric point the concentration of the zwitteer ion is maximum.

The iso – electric point is an individual characteristic of an amino acid and depends on the basicity of
the amino group and the acidity of the carboxyl group, which vary with the nature of the – R group.

e.g. Amino acid Iso – electric Point (pH)

Glycine 6.1

Phenylalanine 5.5

Glutamic acid 3.3

At the iso – electric point the amino acid has minimum solubility. This is the basis of purification and
separation of amino acids/proteins by the process of electrophoresis. A process widely applied in
biochemistry in the separation and purification of proteins.

85
Methods of Isolation of Amino Acids from Proteins
(i) Fractional Crystallisation – one acid in greater proportion and crystallizes faster.
(ii) Fischer’s method – Fractional distillation of esters of amino acids and then
hydrolysing amino acid esters to regenerate the amino acids.
(iii) Selective Precipitation of salts
(iv) Partition Chromatography
(v) Electrical transport methods.

10.8. 0.0 PROTEINS (MACROMOLECULES)

A group of complex organic substances found in nearly all plants and animals.

a) Simple Proteins – Taxonomy

 Albumins: serum albumin, egg albumin, lacto albumin
 Globulins: serum globulin, tissue globulin, vegetable globulin
 Prolamines: zein, (from maize), and gliadin (from wheat)
 Glutelins: gluteline (from wheat), oryzenin (from rice)
 Scleroproteins: keratin (from hair), and fibroin (from silk)
 Histones: from nucleic acids and haemoglobin
 Protamins: (nucleic acids)

b) Conjugated Proteins
They have a non – protein part in their molecule.
(i) Nucleo proteins – nucleic acid (nucleus of the cell)
(ii) Glyco proteins – carbohydrates or its derivatives
(iii) Chromoproteins – have a coloured prosthetic group especially the payrolls
derivatives. The coloured prosthetic group usually contain such metals as Fe, Cu,
and Mg. e.g chlorophyll or haemoglobin.
(iv) Phosphoproteins: have a phosphoric acid residue. E.g. casein (from milk) or viteline
(from egg yolk).
c) Derived Proteins

These are dehydration products which correspond to various stages in the hydrolysis of simple or
conjugated proteins by acid or alkali or enzyme.

e.g. Hydrolysis
Proteins

proteoses peptones polypeptones simple peptides

The substances are synthesised within the plant, from such simple compounds as carbon dioxide,
nitrates and water. When plants are eaten by an animal, the plant proteins are decomposed in the
86
process of digestion and the animal then re-synthesises its own animal protein requirements from the
decomposition products.

These changes play an important role in the nitrogen cycle.

Animal proteins like CHO can act as a source of energy, but they are mainly concerned in the building
up of the animal structures.

Proteins from colloidal solution do not pass through the membrane, which readily coagulate e.g
cooking of egg yolk.

They have very large molecules with high molecular mass

 e.g. Insulin (hormone) = 41,000 (MW)
 Haemoglobin (in blood) = 68,000 (MW)
 Urease (enzyme) = 480,000 (MW)
 Bushy stant virus (plant virus) = 10,000,000 (MW)
 Tobacco mosaic virus protein = 41,000,000 (MW)

PROTEIN SYNTHESIS
Proteins can be synthesised by reaction between amines and carboxylic acids Amino acid molecules
consist of an amino group and a caboxylic acid group.
A dipetide link is as result of condensation between two amino acid molecules, which have the amino
group and the carboxylic acid group.
e.g. glycine + alanine CH3 O H CH3

H2N – CH2 – COOH + H2N – CH – COOH H2N – CH2 – C – N– CH– COOH

GLY ALA GLY – ALA (A dipeptide)

A dipeptide is still an amino acid though not an α – amino acid. It can condense further with another α
- amino acid to give a tripeptide.
e.g. GLY – ALA – LEU.

Long chains of amino acids can be joined to give very long chains of amino acids. Peptides with less
than 100 α – amino acids are called polypeptides. Those with 100 to 10000 or more are proteins.
The peptide link of the proteins or peptides may be broken to give back the original α – amino acids
by
(i) acid hydrolysis
(i) the action of enzymes.
Peptides and proteins are of great importance in the life sciences:-
a) As hormones controlling metabolism and physiology
b) As enzymes regulating metabolic reactions
c) As respiratory pigments transporting oxygen to sites of respiration
d) In the immune response
e) As structural elements in muscles, joints and connective tissues

The table below gives the variation in amino acid composition amongst proteins.

Protein GLY ALA VAL LEU ILE MET PHE TRP LYS

87
Fibroin 44 4 4 1 1 0 3 0 1
(silk)

Keratin 7 4 5 11 0 1 4 2 3
(wool)

Albumin 3 7 7 9 7 5 8 1 6
(hen)

Haemoglo
bin (horse) 6 7 9 15 0 1 8 2 9

Insulin
(ox) 4 5 8 13 3 0 8 0 3

A chain of linked amino acids does not remain in extended form but tends to coil up into an α – helix
form.
Four simple α - amino acids are:-
Glycine (GLY) Alanine (ALA) Serine (SER)
NH2 NH2 NH2
H – C – COOH H – C – COOH H – C – COOH
H CH3 CH2OH
NH2
H – C – COOH
H–C–H
C=C–H
H–C C H
H–C C – OH Tyrosine (TYR)

Two glycine molecules can be united (diaminated) with elimination of water to give glycylglycine (a
dipeptide)
H H O H H O H H O H H O
H – N – C C OH + H – N – C – C OH H N C C N C C OH +H2O
H H H H
2 Glycine Molecules Glycylglycine (a dipeptide)
Such dipeptides have a free - COOH and a free – NH2 group and as such more amino acid molecules
can be linked to it to form tripeptide and polypeptides. (Proteins have molecular masses greater than
10,000)

The linkage between the combined amino acids is

C N– (Peptide link)

O H

With 26 different amino acids, many of them existing in isomeric forms, there are so many ways
(theoretically) by which very large molecules can be built up, This accounts for a wide variety of
naturally occurring proteins.
88
Hydrolysis of different proteins yields a mixture of amino acids.
Alanine can form a protein like structure when the amine grouping reacts with the carboxyl grouping
of a neighbour. A very long chain molecule or polymer is formed (a polypeptide).

- NHCOCH – NHCOCH – NHCOCH –

CH3 CH3 CH3
Nylon is a polypeptide which can be prepared by linking the following molecules

HOOC(CH2)4COOH adipic acid (hexane – 1,6 – dioic acid)

and H2N(CH2)6NH2 hexamethelene diamine

Which gives –
O H O H O H

(CH2)4 C N (CH2)6 C N (CH2)4 C N (CH2)6

This is a condensation polymer in which a molecule of water is given off.

Plants can synthesise the entire range of amino acids. Animals cannot synthesise these amino acids
and are dependent upon plants for essential amino acids
The range of essential amino acids for protein synthesis varies amongst species.

e.g. The Pig requires :-

 Arginine (ARG)
 Histidine (HIS)
 Iso – leucine (ILE)
 Leucine (LEU)
 Lysine (LYS)
 Methionine (MET)
 Phenylalanine (PHE)
 Threonine (THR)
 Tryptophan (TRY)
 Valine (VAL)

Poultry requires all the above and glycine.

The first three letters of the amino acid are used for amino acid identification.

Uses of Proteins
a) For body building (animal life)
b) As synthetic fibres from casein, soya bean, zein.
c) Industrially – natural fibres such as wool, silk.
d) Essential for the working human systems (haemoglobin, various peptide enzymes)
e) Industrially – glue, casein, gelatin.

QUESTION

Combine the following sets of amino acids to get

 Dipeptides HIS + ILE
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  Tripeptides VAL + MET + LYS
 Tetrapeptides PHE + TRY + ARG + LEU
 Polypeptides TRY + THR + GLY + PHE + LYS + GLY + THR
(i) Show clearly the peptide linkages for the combinations
(ii) Write the hydrolysis products of each combination.

NB: Check on the actual structures (molecular) of the amino acids

10.9.0. ALDEHYDES AND KETONES

(ALKANALS AND ALKANONES)

Aldehydes and ketones have the general formula CnH2O and contain the same functional group: - C
= O (carbonyl group)

In aldehydes the remaining two valences of the carbon atom of the carbonyl group are satisfied either
by hydrogen atoms

H–C=O R
H H–C=O
Formaldehyde (General formula)
Or by a hydrogen atom and a hydrogen group.
H
H3C – C = O CH3CHO
Acetaldehyde (ethanal)
In ketones both valences are satisfied by same (simple ketones) or different (mixed ketones)
hydrocarbon groups.
Generally: R e.g CH3 or R’
R–C =O H3C – C = O R–C=O
Simple ketone acetone mixed ketone
O
H3C – C – C2H5 Methyl ethyl ketone
Since ketones and aldehydes are structurally related they have similar methods of formation and
properties.

ALDEHYDES

Aldehyde – an abbreviation for alcohol dehydrogenation.

Or alcohol deprived of hydrogen.
This class of compounds is obtained by dehydrogenation of 1o alcohols (ie removal of hydrogen from
1o alcohols)
They have a functional group – CHO (aldehydic group).

General formula: R – CHO R is any alkyl group or hydrogen

H
Or R–C=O

NOMENCLAATURE
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Formula for aldehyde Corresponding acid Common name IUPAC system
(aldehyde)
H.CHO HCOOH Formaldehyde Methanal
(formic acid)
CH3CHO CH3COOH Acetaldehyde Ethanal
(acetic acid)
C2H5CHO C2H5COOH (propionic Propionaldehyde Propanal
acid)
C3H7CHO C3H7COOH Butyraldehyde Butanal
(butyric acid)
C4H9CHO C4H9COOH Valeraldehyde Pentanal
(valeric acid)

NB The common system of naming the aldehydes is by considering the name of the acid produced
when the corresponding aldehyde is oxidised . The ending ‘ic acid’ is replaced by the suffix
‘aldehyde’.
In the IUPAC system the name of the corresponding alkane has the terminal ‘e’ replaced by ‘al’.

KETONES
They have a general formula: R – C = O
R’
R and R’ represent either identical or different alkyl groups.

The C = O is the ketonic group

Nomenclature

Common System – named according to the alkyl group(s) attached to the ketonic group.

O O

e.g. Symmetrical ketones H3C – C – CH3 H5C2 – C – C2H5

Dimethyl ketone (acetone) Diethyl ketone

For unsymmetrical or mixed ketones they are named by naming the two hydrocarbon groups attached
to the functional (ketonic) group separately first naming the simple group.
O
H3C – C – C2H5
Methyl ethyl ketone
In IUPAC system, the longest carbon chain containing the ketonic group is taken as the parent chain.
The ending ‘e’ of the alkane is replaced by ‘one’ in ketones.
e.g Butane as a ketone is butanone
Pentane as a ketone is pentanone

O
H3C – C – C2H5 2 – Butanone
O O
H3CH2C – C – CH2 – CH3 H3CCH(CH3) – C – CH2 – CH2 – CH3
3 – Pentanone 2 – Methyl – 3 – hexanone
H3C – C – CH = CH – CH3
O 3 – Penten – 2 – one
Physical Properties of Aldehydes and Ketones
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They exhibit the normal gradation of the members of any homologous series.
 Formaldehyde is a gas
 Acetaldehyde is colourless volatile liquid
 Higher members in the series are solids

Chemical Properties
Formaldehyde chemically behaves differently from other aldehydes because it does not contain any
alkyl groups.
a) Oxidation to fatty acids – It is readily oxidised to corresponding fatty acids.

Generally : RCHO [O] RCOOH

E.g. HCHO [O] HCOOH

Formaldehyde formic acid

CH3CHO [O] CH3COOH

Acetaldehyde acetic acid

b) Reduction to primary alcohols – Except formaldehyde, other aldehydes are reduced to 1o alcohols

Generally : RCHO [2H] RCH2OH

E.g. CH3CHO [2H] CH3CH2OH

Polymerization
Aldehydes readily polymerise yielding products very varied, depending on the aldehyde and the
conditions.

1) Paraformaldehyde – (HCHO).H2O
- Obtained when aqueous solution of aldehyde is evaporated.
- A white powder – a polymer of formaldehyde is formed.

2) Metaformaldehyde – formed when gaseous, or liquefied formaldehyde is cooled.

- Can also be obtained if 60% of aqueous solution of the aldehyde is reacted with 2% H2SO4 forming
a white crystalline solid known as Metaformaldehyde or trioxy methylene or trioxane.
H2
O C
3HCHO H2C O
O C
H2
3) Formose (HCHO)6

- Formed by polymerisation of formaldehyde in the presence of lime water. Fructose (C6H12O6) is one
of the components of the mixture. This polymerisation is one of the stages in which carbon dioxide is
converted into sugars in plants during photosynthesis.

Reactions of Aldehydes with Bases (Alkalis)

Self Reduction/Oxidation of Aldehydes

i) Formaldehyde undergoes self reduction – oxidation reaction when reacted with 50% aqueous alkali.
 One molecule - is oxidised to formic acid
 One molecule – is reduced to methanol
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2HCHO + NaOH HCOONa + CH3OH
Formaldehyde sodium formate methanol
Cannizaro’s Reaction

The aromatic aldehydes also undergo Cannizaro’s reaction.

CHO CH2OH COOK
+ KOH +

Benzaldehyde Benzyl alcohol Potassium benzoate

Reactions of Ketones

Acetone:
- Produces iso – propyl alcohol or pinacol (tetramethyl ethylene glycol when reduced.
O H
H3C – C – CH3 + H2 H3C – C – CH3

OH (iso – propyl alcohol)

CH3 CH3
H3C – C = O H3C – C – OH
H3C – C = O + H2 H3C – C – OH (Pinacol)
CH3 CH3

Chloroform reacts with ketones in the presence of caustic potash to form chlorohydroxy compounds.
CH3 OH
H3C – C = O + CHCl3 KOH H3C – C – CCl3
CH3
1, 1, 1 – trichloro – 2 – methyl propan – 2 – ol
Uses of Aldehydes and Ketones
a) Methanal
1) In the manufacture of thermosetting plastics, in particular Bakelite, carbamide
– methanal resins and polyxymethylene.
2) In solution (formation) it is used as a disinfectant and to prepare animal specimens

b) Ethanal
In the manufacture of ethanoic acid
c) Propanone
o In the manufacture of Perspex
o As a solvent for plastics, varnishes and greases.

15.0.0 CARBOHYDRATES
Carbohydrates are polyhdroxy aldehydes (aldoses) or polyhdroxy ketones (ketoses) or such
compounds which yield these on being hydrolysed.
Carbohydrates have at least one asymmetric carbon in their molecular structures.

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They are the most abundant in nature.

Examples of carbohydrates are:-

 Cane sugar
 Glucose
 Starch
 Cellulose

They are of great importance in the daily diet. They play an essential part in the metabolism of all
living organisms.

Starch – a polysaccharide, is the principal form in which energy is stored b plants.

Cellulose – also a polysaccharide, forms a principal structural material of plants.
Paper, plastics, synthetic fibres, photographic films, explosives are all cellulose derivatives.
In the Diet – there is starch, sugar, and glucose

Many carbohydrates have a general formula :- Cx(H2O)y

Ratio of oxygen to hydrogen 1 to 2 (as in water – H2O)
Carbohydrates are hydrates of carbon (Hydrate de Carbon – in French)

Compounds which have a formula Cx(H2O)y but are not carbohydrates are:
 Formaldehyde (CH2O)
 Acetic acid (C2H4O2)
 Lactic acid (C3H6O3)

The source of carbohydrates for both human food and other commercial uses are plants.
Carbohydrates can therefore be defined as polyhydroxy aldehydes or ketones or such compounds
which yield these on hydrolysis. They have at least one asymmetric carbon atom in their molecule.

The source of carbohydrates for both human food and other commercial uses are plants. Plants
synthesise the carbohydrates from carbon dioxide and water by photosynthesis. They use it as an
oxidizable fuel (source of energy), store it for later use as a fuel e.g. starch in potatoes or grain and
glucose in sugar beet or sugarcane

CLSSIFICATION OF CARBOHYDRATES

CARBOHYDRATES

SUGARS POLYSACCHARIDES
(C6H10O5)n

MONOSACCHARIDES DISACCHARIDES
(C12H10O5)

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PENTEOSES HEXOSES
(C5H10O5) (C6H12O6)

MONOSACCHARIDES

Many of the monosaccharides occur naturally. Others are synthetically prepared. The sugars
containing up to 10 carbon atoms have been obtained synthetically.
Characteristics
(i) Monosaccharides have a sweet taste.
(ii) They char on heating
(iii) They are optically active

Trioses (C3H6O3)

(i) Glyceraldehyde, the only known aldotriose.

- it has only one asymmetric carbon
- it exists in two optically active forms

CHO CHO

H C OH HO C H

CH2OH CH2OH

Glyceraldehyde is chosen as a standard for determining the configuration in sugar chemistry.

All the sugars which have the D – asymmetric carbon drawn at the base belong to the D – series.
Those which have the L – glyceraldehydes asymmetric carbon at the base belong to the L – series.

(ii) Tetroses (C4H8O4)

An aldotetrose has a formula: CH2OH.CHOH.CHOH.CHO

- it has 2 asymmetric carbon atoms
- it is capable of 4 optically active forms (D – and L – Erythrose, and D – and L -
Threose)

CHO CHO CHO

H C OH HO C H C=O

H C OH H C OH H C OH

CH2OH CH2OH CH2OH

D – Erythrose D – Threose D – Erythrulose

A ketotetrose has only one asymmetric carbon atom.

It exists in two optically active forms, the D – and L – Erythrulose.

(iii) Pentoses (C5H10O5)

CHO CHO CHO CHO

95
H C OH HO C H H C OH HO C H

H C OH H C OH HO C H HO C H

H C OH H C OH H C OH H C OH

CH2OH CH2OH CH2OH CH2OH

D – Ribose D – Arabinose D –Xylose D – Lyxose

Only D – Arabinose, D – Ribose, D – Xylose, L – Arabinose occur in nature, others are synthetic.

Ketopentoses, CH2OH.CO.CHOH.CHOH.CHOH.CH2OH.
- have only two asymmetric carbon atoms
- they exist in 4 optically forms – D - and L – Ribulose and Xylulose.

iv) Hexoses. Aldohexoses have 4 asymmetric carbon atoms in their formula.

CH2OH.CHOH.CHOH.CHOH.CHOH.CHO
They can exist in 16 optically active forms.
D – and L – forms of Glucose, mannose, Allose, Altrose, Gulose, Idose, Galactose, and Talose.

Ketohexoses. They have 3 asymmetric carbon atoms in their formula.

CH2OH.CO.CHOH.CHOH.CHOH.CH2OH.
They exist in 8 optically active forms. D – and L – Fructose, D – and L – sorbose, D – Tagatose, L –
Psicose.

GLUCOSE (DEXTOSE, GRAPE SUGAR) – C6H12O6

The glucose molecule has one aldehydic group, one alcoholic primary group and in all 5 hydroxyl
groups.

Configuration or Stereochemistry of Glucose.

The open chain structure of glucose below contains 4 asymmetric carbon atoms (carbon atoms 2, 3,
4, and 5)
Glucose represents sixteen possible stereoisomers for which only one represents glucose.

H H H H H

CH2OH C C C C C=O

OH OH OH OH

Occurrence:- In sweet fruits and particularly in grapes.

- In di, and polysaccharides in combined state
Maltose, starch and cellulose are built up entirely of glucose units. Hydrolysis of these carbohydrates
yields only glucose molecules
Glucose is present in constant amount in blood and in urine of animals. In diabetic patients, the sugar
level may be as high as 3 to 10%.
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Uses of Glucose
 As food for patients and growing babies or weak persons
 In preparation of sweets, candies, syrups, and confectionary,
 For the preparation of beer and wine
 In preparation glycerol,
 In preparation of Vitamin C industrially,
 In silvering of mirrors and vat – dying as a reducing agent,
 As an intravenous injection to the patients for patients with lower glucose content in blood,
 In the processing of tobacco.

FRUCTOSE (FRUIT SUGAR) – C6H12O6

Fructose has three asymmetric carbons in the molecule. It exists in 8 isomeric forms.

Open Structure of Fructose

H H H H H

CH2OH C C C C C C H

OH OH OH OH O OH.

Occurrence:- very abundant in fruits (fruit sugar). With glucose, it is present in cane sugar and
honey.
The polysaccharide insulin gives only D – fructose on hydrolysis.
It is laevorotatory and it is therefore known as laevulose.

Laboratory Preparation
- Hydrolysis of cane sugar

C12H22O11 + H2O H2SO4 C6H12O6 + C6H12O6

Cane sugar Glucose Fructose
A solution of cane sugar is boiled with dilute sulphuric acid till the hydrolysis is complete.

Uses
 In confectionary as a sweetening agent
 As a sweetening agent for diabetic patients since is easily assimilated.

DISACCHARIDES

These yield two monosaccharides.

General formula for those that yield two hexoses on hydrolysis is:
C12H22O11
The three disaccharides are isomeric (C12H22O11)

The products of hydrolysis can either be the same or different.

e.g. C12H22O11 H2O C6H12O6 + C6H22O11

Sucrose Glucose Fructose

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Lactose H2O Glucose + Galactose

Maltose H2O Glucose + Glucose

The enzymes that bring about the hydrolysis of the disaccharides are:

Sucrose Invertase
Lactose Lactase
Maltose Maltase

Sucrose is the most important. It is an essential constituent of our diet.

SUCROSE OR CANE SUGAR (C12H22O11)

Occurrence: - In plants e.g. sugar cane and sugar beet (beet sugar)
- also in fruits like ripe bananas, ripe mango, apricot, pine apple,

Hydrolysis: When boiled with dilute acids or hydrolysed with an enzyme invertase the sucrose yields
equimolecular mixture of glucose and fructose.

C12H22O11 + H2O C6H12O6 + C6H12O6

Cane Sugar Glucose Fructose
[α]D = 66.5 [α]D = +52.7 [α]D = -92.4
Net result is laevorotation
Sucrose is dextro – rotatory. On hydrolysis it produces dextro – rotatory glucose and laevorotatory
fructose. The rotation of fructose is greater than that of glucose. The mixture is therefore laevo –
rotatory. There is a change inversion) in the rotation of the reaction mixture from dextro – rotation to
laevo – rotation and thus the inversion is brought about by the enzyme invertase.

Structure of Sucrose Molecule

CH2OH O
O
H H H HOCH2 H

OH OH H O H OH CH2OH

H OH OH H

Uses: -
 As a sweetening agent for various food preparations, sweets, candies, jams, syrups.
 In food preservation
 In the manufacture of sucrose octa – acetate used in the manufacture of transparent papers
and anhydrous adhesives.

LACTOSE, MILK SUGAR, C12H22O11

It is fond in the milk of animals and humans.

 Cows milk has 4% of lactose
 Human milk contains about 7% of lactose
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Properties
 It is a white crystalline
 It is soluble in water
 It is insoluble in ether, alcohol, benzene and other inorganic solvents
Lactose is dextrorotatory and exhibits mutarotation.
The α – form has an M.P. of 203oC, with rotation of [α]20D = +89.5 and the [β]20D = +35o, M.P = 252oC
(with decomposition)
The equilibrium value for specific rotation is +35.5o. he molecules crystallise as monohydrates.
Lactose is hydrolysed by dilute acids and emulsion into glucose and galactose
.
C12H22O11 + H2O C6H12O6 + C6H12O6
(+) Lactose (+) Glucose (+) Galactose

Lactose hydrolyses by emulsion (β – glycosidic linkage splitting enzyme).It shows that lactose is β –
glycosidic.

Molecular Structure of Lactose

CH2OH H OH
O
OH H O OH H H

H OH H H H H OH
O
H OH CH2OH

Uses of Sucrose:-
(i) In homoeopathic and biochemic medicine in preparation of pills and tabletys
(ii) As food ingredient for infants and invalids
(iii) In the manufacture of beer to improve its flavour
(iv) In the mould substrate in penicillin manufacture
(v) In the preparation of lactic acid, butyl alcohol, acetone.

MALTOSE, (MALT SUGAR), C12H22O11

- Present in sprouted grain. It is produced as a result of hydrolysis action of diastase on

starch.
Properties
 It is soluble in water; the solution is monohydrate, in fine needles, separates out.
 It shows mutarotation The α – form has [α]20D = + 168o and β – form = +112o. the equilibrium
value is +136o
 On acid or enzymic hydrolysis with maltase the sugar yields D – glucose

C12H22O11 + H2O 2C6H12O6

Molecular Structure of Maltose

CH2OH CH2OH
O H H O
H H H H

HO OH H OH H
99
 O OH
H HO H OH

POLYSACCHARIDES
They have a general formula: (C6H10O5) n can have a value from 12 to a few thousands
- They are natural polymers.
- Generally they are tasteless and amorphous compounds
- They are insoluble in water
- They form colloidal solution
- When hydrolysed with dilute acids or enzymes they yield monosaccharides often
forming various oligosaccharides as intermediates.

STARCH, AMYLUM (C6H12O5)n

- Widely distributed in vegetable kingdom. in nature it is transformed into complex polysaccharides

like gums, and cellulose. It is also transformed into simpler mono and disaccharides by enzyme
working in vegetable kingdom.

The rich sources are :-

 Potatoes Wheat, Rice, Maize, barley, Arrow root

Properties

 It is white, amorphous substance with no taste or smell

 It is insoluble in water but when added to boiling water the starch granules swell and burst
forming colloidal, translucent suspension.
 Starch when boiled with dilute acid, yields glucose as final product

(C6H10O5)n (C6H10O5)n1 C12H22O11 C6H12O6

Starch Dextrin Maltose Glucose

When hydrolysed with the enzyme diastase, maltose is obtained.

2(C6H10O5)n + H2O Diastase nC12H22O11

Starch Maltose

Starch solution gives a blue colour with a drop of iodine solution. The blue colour disappears on
heating and reappears on cooling. .

Uses of Starch
 An important part of the diet as rice, bread, potatoes, arrow root
 In the manufacture of starch jelly and adhesives
 A valuable source of glucose and alcohol
 In laundry for softening linen
 In paper and textile industries
 As an indicator for iodometric titrations
 In preparation of soluble starch, starch acetate, nitro – starch

CELLULOSE

Occurrence:-
100
 - Widely distributed in plant kingdom. Plants maintain their structure due to support of
fibrous material which is starch.
- Cotton is almost pure cellulose
- Jute, hemp, wood paper are all different forms of cellulose.
Properties:

(i) A colourless amorphous substance of the source of starch

(ii) Has organised fibrous structure,
(iii) It is insoluble in water
(iv) It dissolves in ammoniacal solution of cupric hydroxide
(v) Cellulose also dissolves I zinc chloride in hydrochloric acid.
(vi)When the cellulose is treated with concentrated sulphuric acid, in cold it slowly passes into
solution. The solution when diluted with water, precipitates a starch like substance amyloid.

3) When boiled with dilute sulphuric acid it is completely hydrolysed into D – Glucose

(C6H10O5)n + nH2O C6H12O6

Cellulose Glucose

The enzymic hydrolysis of cellulose yields a disaccharide cellobiose having the glucose units linked
through the 1,4 – β - glycosidic linkages.

Uses:
a) In the manufacture of paper, cloth
b) Cellulose nitrates in the manufacture of explosives, medicines, paints, and lacquers
c) Cellulose nitrates with camphor yields celluloid which is used in manufacturing toys,
decorative articles and photographic films
d) Cellulose acetate is used in rayon manufacture and in plastics.

10.10 PHENOLS

They have the hydroxyl functional group attached to the aromatic ring.
Simplest member of the series is phenol or carbolic acid. OH

OH (Phenol)
OH 1, 2 – dihydroxy benzene
or orthodihydroxy benzene

Acid/Base Properties
A phenol is normally considered to be an acid. It readily forms salts with alkalis and alkali metals.
OH O-
+ H2O + H3O+
Phenols are more acidic than alcohols
Phenol Ka = 10 -10
Aliphatic alcohol Ka = 10 to 10-18
-13

Redox Reactions

Phenols are more readily oxidized than alcohols.

OH O

[O] p - benzoquinone

101
 O
The products of oxidation are normally highly coloured quinines (cyclic diketones). Such type of
reaction is employed in photographic development. The silver bromide on the exposed film is
precipitated as silver by the redox reaction.

OH O
+ 2Ag+ + 2OH- . 2Ag + 2H2O +

O
Uses of Phenols

o Phenol itself was the first antiseptic

o The phenol is the starting point for the industrial synthesis of many drugs, dyes and plastics.

PESICIDES, PCBs AND DIOXINS

Pesticides are chemical substances used to kill organisms (bacteria, fungi, insects, nematodes, rats,
birds) which consume, damage or destroy agricultural products, either in the field or during or during
storage. They are complex organic compounds with long and cumbersome systematic names.

e.g DDT C14H9Cl5 (dichlorodiphenyl trichloroethane)

or 1, 1, 1 – trichloro – 2, 2 – di – (4 – chlorophenyl) ethane

H
Cl C Cl
CCl3

Naturally Occurring Organic Insecticides

These are plant and animal extracts.

e.g.- (i) Nicotine – an alkaloid from tobacco
Use :- In the fumigation of green houses

(ii) Pyrethrum extracts from the flowers of pyrethrum cinerariaefolium (grown in East Africa).
There are several active ingredients including pyrethrin - 1 (C12H28O3) . It has a rapid ‘knock down’
activity and low toxicity to mammals. Pyrethrum is therefore an important insecticide e.g. in household
sprays and in horticulture. They have unsaturated aliphatic structures which undergo rapid
photolytically induced oxidation.
Extracts from several Derris Species (from South America).
Active ingredient : Rotenone (C23H22O6). – It has low toxicity; applied in horticulture.
Nicotine, pyrethrum and Derris are non – persistent ; they break down to harmless residues within a
few hours of application.
Also hydrocarbon oils (aliphatic and aromatic) have been used to kill insects and mites.

(b) Organochlorine Insecticides

A group of synthetic insecticides which includes, a variety of aromatic and non – aromatic
compounds, all containing chlorine. Due to the aromatic nature of some of these compounds and the
102
lack of hydrophilic groups in all members, these pesticides are highly hydrophobic and vary resistant
to chemical degradation.

e.g. DDT - has low mammalian toxicity.

It was widely used for public health applications (against malaria mosquitoes) and in agriculture,
horticulture and forestry.

Properties of DDT:

- It is unreactve and hydrophobic.

- Its residues are extremely persistent in the environment and tend to accumulate in the lipid stores of
long – lived mammals and birds. Other later formulated organochlorine compounds caused more
problems.

e.g. Diedrin (C12H8Ol 6).

It is used for seed treatment and sheep – dip caused widespread mortality amongst birds eating
newly grown grain, and in predatory birds, due to the persistence of the pesticide.
Other restricted pesticides are - aldrin, heptachlor, endosulphun,and endrin. Lindane or gammoxene
is still in use due to its lower mammalian toxicity and more break down in the soils and tissues.
Use;- for control of pests in food crops such as potato (need to purify it).

(b) Organophosphorus Insecticides

They are also aliphatic and aromatic compounds containing phosphorus They kill insects by
disruption of the nervous system This group of insecticides are easily hydrolysed and are therefore
less stable chemically than the organochlorines. They tend to be degraded to harmless residues
within hours of application. Their reactivity makes the organophosphorus compounds harmful to
mammals by interfering with enzyme function. So the group of insecticide can cause acute toxicity
and death (of humans, livestock and wildlife) at the time of application if not applied carefully and
safely.

Mechanism of Action

The toxic action takes place at the synapses, or junction between nerve cells, where impulses are
chemically transmitted (by acetylation of choline). When functioning normally, the reaction is rapidly
reversed through the action of cholinesterase, so that stimulation ceases and the site is ready to
receive a new impulse. The nerve poisons act by inhibiting (blocking) cholinesterase which leads to
failure of the nervous transmission, convulsions and death.. Nicotine has a similar reaction, blocking
cholinesterase.

Individual Members of Organophosphorus Pesticides

(a) Parathion

Used in agriculture; effective against aphids and red spider mites

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It is a pro - insecticide i.e it is toxic to those animals whose MFO (Mixed Function Oxidases) can effect
the change into oxyphosphate.

(b) Malathion

It is less toxic than malathion

Used for protection of wide range of crops such as cotton, fruits, potatoes, rice, vegetables, stored
grain, mammalian parasites
It is marketed under the cloak of 29 different trade names.

c) Iodofenphos

It is a contact insecticide
It has systematic properties i.e. it is translocated in plants and it persists long enough to make the
host itself toxic to insects that it or suck it.

(d) Dichloros

It is very volatile and therefore it is incorporated into slow release insecticidal strips for control of flies,
moths, mosquitoes.
It is effective to plants against sucking insects
It is not persistent being rapidly hydrolysed.

(e) Glyphosate

It is used as a herbicide
In soil, as an insecticide
It blocks normal development in peptides where it acts as a glycine mimic.
It has 20 trade names.

(f) Chloropyrifos

It is used in such major crops as citrus fruits, coffee, cotton, maize and also against the mosquito.
It persists only for 60 to 120 days.

Most of these are used in the field of agriculture and households. They have to be handled with
maximum care as they are very harmful to humans and other living organsms. They can be very
lethal.

Unit summary

In this unit you worked through a number of concepts reactions and mechanisms that provide
underpinning knowledge about saturated and unsaturated hydrocarbons as well as environmental
awareness of the products you have studied the following:-

(a) The general unreactivity of alkanes

(b) The reactions of alkanes

i combustion
ii substitution reactions.
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(c) Addition mechanisms of chlorines
(d) Addition reactions of alkenes
(e) Oxidation of alkanes.
(f) The source of alkanes and purification
(g) Substitution reactions of benzene.
(h) The mechanisms of electrophilic substitution in arenes

ENVIRONMENTAL CHEMISTRY
Introduction
Welcome to unit 3 Environmental management. This is very important topic because it covers all
aspects of chemical reactions. You will focus on atmospheric pollution and water pollution. In addition
you will look at land pollution because that is your main resource as Agriculturist. You are supposed
to critically study ways of trying to reduce pollution.

Unit objectives

Upon completion you shouted be able to

i. Outlined the role of ozone in the strata sphere

ii. Recognise carbon dioxide, sulphur dioxide, oxides of nitrogen and lead compounds may be
released as a result of combustion of hydrocarbons based fuels.
iii. Outline problems associated with the release of pollutants.
iv. Recognise the problems associated with heavy metals in the environmental, typically by lead.
v. Describe the damages waste and oil spillages have on water

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Introduction to Environmental Management

Having looked at useful reactions of hydrocarbons and inorganic compounds, you are now going to
study environmental problems associated with these reactions.

11.1 Atmospheric pollution.

There are a range of atmospheric pollution problems currently threatening the earth’s general
environment.

11.1.1 Acid rain

You will find that the acidic gases produced by burning fossil fuels in a number of different situations
create a lot of problems.

You will find that the majority of power stations in industrialized countries burn coal or oil. Both these
fuels are contaminated with sulphur which produces sulphur oxides when it burns:-

S(s) + O2g SO2(g)

Oxides of nitrogen (NOX) (for example nitrogen dioxide NO2) are produced when air furnaces or in
vehicle petrol engines.

These gases produced dissolve in rain water to produce acid rain.

You will encounter numerous effects of acid rain.

 Limestone buildings, statues and so on are worn out.

 Lakes are acidified, and the presence of metal ions (for example Al3+ ions) reached
(washed) out of the soil damages the gills of fish. The fish can die.
 Nutrients are reached out of the soil and from leaves. You will find that trees are
deprived of these nutrients. Aluminum ions are freed from clays as aluminum sulphate
and damage tree roots. The tree is unable to draw up enough water through the
damaged roots, and it dies.

The wind can carry acid rain clouds away from the industrialized centres, carrying the pollution to fall
on the other countries.

You need to take remedial measures for the effects of acid rain are limited and expensive to carry out.
You can add lime to lakes and the surrounding land, to decrease the acidity. Although they are useful
and beneficial in the long term. Petrol (gasoline) for example for cars has now been made almost free
of sulphur.

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Fuel – gas desulphurises can be fitted to power station and factory to reduce the levels of sulphur
dioxide.

Global warming - the green house effect. You will notice that the presence of water vapour, carbon
dioxide and other gases in the air has served the world well.

The trapping of heat by the atmosphere has kept the earth warm. Without this green house effect, the
average temperature of the earth’s surface would be – 18oC, rather than 15oC. However, you will
discover that high levels of certain gases produced by human activity are increasing this heating
effect and producing global warming.

The “green house gases” that produce this warming include water vapour, carbon dioxide, methane,
the oxides of nitrogen and chlorofluorohydrocarbon - carbons). These gases absorb heat from the sun
that is reflected from the earth’s surface becomes warmer. Our dependence on fossils fuels for
energy and transport means that the levels of carbon dioxide released into the atmosphere are very
high. Large – scale deforestation, particularly of the tropical rain forests to provide land for Agriculture,
also increases the level of carbon dioxide in the air because it removes trees.

This absorbs the gas for photosynthesis. The effects global warming are complex. The polar ice –
caps would begin to melt as the temperature rises. The increase in sea level would threaten low lying
lands that a reduction of 30 – 60% in CO2 is needed to keep the present temperature balance.

11.1.3 Ozone Layer Depletion.

A protective layer of ozone in the stratosphere prevents harmful uitra – violent radiation reaching the
earth’s surface. However, research has shown that, this ozone layer has depleted, particularly over
Antarctica. The ozone hole has grown large over recent years. CFC’s and other halogen compounds
are thought to cause the damage.

11.1.4 Local Atmospheric Pollution

You will also encounter various types of pollution that occur over smaller, local areas. There usually
large cities, where there is heavy use of motor cars. These forms of pollution are:

 Photo chemical smog

 High levels of carbon monoxide and
 High levels of lead compounds.

11.1.5 Photochemical smog:-

Is formed in regions where there is a large amount of traffic. Severe photo chemical smog often
occurs in cities located in valleys or surrounded by hills or mountains. On sunny, windless days,
oxides of nitrogen are trapped by the hills in air that is close to the ground that is low to the ground.

A complicated series of reactions take place and ground – level ozone is one of the products. In these
circumstances ozone is harmful, particularly for asthma sufferers.

11.1.6 Carbon monoxide

Is a common pollutant you will have in industrialized world. It is produced when hydro carbon fuels are
not completely burnt.

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Carbon monoxide is poisonous at levels of only 0.1%. Oxygen is very important to living things. In our
bodies it is carried round the body attached to haemoglobin in our red blood cells carbon monoxide is
attracted more than oxygen. In blood, carbon monoxide prevents haemoglobin from carrying oxygen.
This leads to dizziness and headaches if you are exposed to carbon monoxide for a long time leads to
death.

Lead compounds are the most toxic heavy metal pollutant you will find in the air. Lead compounds
form part of the urban dust that forms in a city atmosphere, people living next to busy roads can have
high levels of lead in their blood. This has been linked with nervous disorders and with learning
disabilities in children. The increase) moves to use unleaded petrol are reducing this health hazard.

11.1.7 Water Pollution.

You will hear people say “water is life” this is because water is major resource that is essential to our
life. However, as with atmosphere, we are continually guilty of polluting the rivers and oceans.
Industrial waste has been pumped into rivers in spite of legal restrictions. Many pollutants are
involved, but among the most dangerous are the mercury. These can have disturbing effects on living
things even at low levels they can also pass from one living thing to another along the food chain and
effect life at various levels in the chain.

Industrials and power stations use water from rivers as coolant. When this water is returned to the
river at higher temperature is causes thermal pollution. Less oxygen can dissolve in this warm water,
so that plants and animals in the water have greater difficult in breathing. Sewerage, detergents and
run off fertilized fields can all reach rivers and cause damage to plant and acquatic life. Italian
resorts in the Adriatic have in the past been troubled by green slime. This slime was due to the flow of
effluent (waste) from the delta of the river Po.

Pesticides also pose problems, if you do not dispose them professionally, as concentrated through
the food chain in fish. Apart from dangers to fish stocks the concentration of cancer – causing
chemicals at stages in the food chain is a source of greater concern.

You heard several major spills at sea, with the release of thousands of tones of crude oil into the
marine ecosystem. The immediate effect of oil continues to do more unseen damage after being
broken up into small droplets. These are absorbed by sea fish and microorganisms and so enter the
food chain.

ACTIVITY 6

1. What do you understand by the term environmental?

2. Mention the main sources of air pollution.
3. How can a farmer help in reducing pollution?

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Unit Summary

In this unit, you worked through environmental concerns in terms of air pollution, water pollution and
land pollution. You have been challenged to contribute in controlling pollution. Above all you have
studied the following:-

a. The environmental consequences of carbon monoxide, oxides of nitrogen and unburnt

hydrocarbons from car emissions.
b. Problems associated with pollution of water and air.
c. use of catalytic converters and unleaded fuels as means to reducing pollutions.
d. Acid rain as a result of atmospheric pollution.
e. Water pollution
f. Concepts such as
i. Photo chemical smog
ii. Lead compounds
iii. Carbon monoxide as pollutant
iv. Thermal pollution

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