Secondary

Chemistry
Form Three
Students’ Book
(Third Edition)
KENYA LITERATURE BUREAU
P. O. Box 30022-00100, Nairobi
Website: www.klb.co.ke
E-mail: [email protected]

© Ministry of Education
All rights reserved. No part of this book may be reproduced, stored in a retrieval system, or transcribed in
any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the
prior written permission of the publisher.

ISBN 978-9966-10-007-8

First published 1988

Reprinted 1988, 1989, 1990, 1991, 1993, 1994, 1995(twice), 1996, 1997, 1998, 1999, 2000, 2001, 2002,
2003, 2004
Second Edition 2004
Reprinted 2004, 2005(thrice), 2006, 2007(twice), 2008(thrice), 2009(five times), 2010(twice), 2011
Third Edition 2011
Reprinted 2011(twice), 2012(wice), 2013(twice)

KLB 11398 30m 2013

Published and printed by Kenya Literature Bureau

 Prologue
This Students’ Book has been written to assist Form Three Chemistry students.
The book meets all the requirements of the current syllabus. It also conforms to
current international trends in the teaching of the subject.
Chemistry is a practical subject which equips students with concepts and
skills that come in handy in solving day-to-day problems. Chemistry aims at
providing the learner with the necessary knowledge for the benefit of an
individual in their day-to-day life and for further education. This book
recognises these aspects and provides adequate practical exercises to sharpen the
students’ manipulative skills. In addition to the end of topic questions, this
edition includes two complete examination style sample papers for self
evaluation.
The book is written in a clear, concise language and is part of the Secondary
Chemistry Series.

The Managing Director,

Kenya Literature Bureau
 Contents
Prologue
Acknowledgements
1. Gas Laws
Boyle’s Law
Charles’ Law
Combined Gas Law
Standard Conditions
Diffusion and the Graham’s Law
Summary
Revision Exercise

2. The Mole: Formula and Chemical Equations

Relative Mass
Inter conversion of Molecules and Moles
Inter conversion of mass and moles
Empirical and Molecular Formula
Empirical Formula
Molecular Formula
Molar Solutions
Concentration of a Solution
Preparation of Molar Solutions
Dilution of a Solution
Stoichiometry of Chemical Equations
Volumetric Analysis
Titration
Back Titrations
Redox Titration
Atomicity and Molar Gas Volume
Combining Volumes of Gases
 Summary
Revision Exercise

3. Organic Chemistry I
Alkanes
Cracking of Alkanes
Nomenclature
Isomerism in Alkanes
Laboratory Preparation of Alkanes
Physical Properties
Chemical Properties
Uses of Alkanes
Alkenes
Nomenclature
Isomerism in Alkenes
Laboratory Preparation of Ethene
Physical Properties
Chemical Properties
Tests for Alkenes
Uses of Alkenes
Alkynes
Nomenclature
Isomerism in Alkynes
Laboratory Preparation of Ethyne
Physical Properties
Chemical Properties
Test for Alkynes
Uses of Alkynes
Summary
Revision Exercise

4. Nitrogen and it’s Compounds

Isolation of Nitrogen Gas from Air
Laboratory Preparation of Nitrogen Gas
 Oxides of Nitrogen
Nitrogen(I) Oxide
Nitrogen(II) Oxide
Nitrogen(IV) Oxide
Ammonia
Laboratory Preparation of Ammonia
Solubility of Ammonia in Water
Large Scale Manufacture of Ammonia by Haber Process
Uses of Ammonia
Nitrogenous Fertilisers
Nitric(V) Acid
Laboratory Preparation of Nitric(V) Acid
Industrial Manufacture of Nitric(V) Acid
Reactions of Dilute Nitric(V) Acid
Reactions of Concentrated Nitric(V) Acid
Uses of Nitric(V) Acid
Nitrates
Action of Heat on Nitrates
Test for Nitrates
Pollution Effects of Nitrogen Compounds in the Atmosphere
Summary
Revision Exercise

5. Sulphur and its Compounds

Extraction of Sulphur
Allotropes of Sulphur
Physical Properties of Sulphur
Chemical Properties of Sulphur
Oxides of Sulphur
Preparation of Sulphur(IV) Oxide
Physical Properties of Sulphur(IV) Oxide
Chemical Properties of Sulphur(IV) Oxide
Bleaching Action of Sulphur(IV) Oxide
 Reducing Action of Sulphur(IV) Oxide
Oxidising Action of Sulphur(IV) Oxide
Preparation of Sulphur(IV) Oxide
Test for Sulphate and Sulphite Ions
Uses of Sulphur(IV) Oxide
Large Scale Manufacture of Sulphuric Acid
Properties of Sulphuric Acid
Reactions of Dilute Sulphuric Acid
Hydrogen Sulphide
Chemical Properties of Hydrogen Sulphide
Pollution of the Atmosphere by Compound of Sulphur
Summary
Revision Exercise

6. Chlorine and its Compounds

Preparation of Chlorine
Physical Properties of Chlorine
Chemical Properties of Chlorine
Oxidising Properties of Chlorine
Reaction of Chlorine with Alkaline Solutions
Test for Chloride Ions
Uses of Chlorine and its Compounds
Hydrogen Chloride: Laboratory Preparation
Chemical Properties of Hydrogen Chloride
Large Scale Manufacture of Hydrochloric Acid
Uses of Hydrochloric Acid
Environmental Pollution by Chlorine and it’s Compounds
Summary
Revision Exercise
Sample papers
Appendices
 Acknowledgements
The Managing Director, Kenya Literature Bureau would like to thank the
following writers who participated in the revision of this edition of the
Secondary Chemistry Form Three Students’ Book:
Cornelius Masila – Mukaa Secondary School, Nunguni
Muange
Emma Achieng Ogutu – Moi Girls’ High School, Eldoret
Raphael Kelly – Ikanga Secondary School, Kitui
Wambua
Rose Amatikide Emoru – Bunyore Girls’ Secondary School, Maseno
Silas M. Mango – St. Cecilia Misikhu Girls’ High School, Webuye
 Chapter Gas Laws
1
By the end of this Chapter, the learner should be able to:

(a) State Boyle’s and Charles’s laws.

(b) Describe experiments to illustrate Boyle’s and Charles’ laws.
(c) State and use the combined gas law to solve numerical problems.
(d) State Graham’s law of diffusion and relate the rate of diffusion to relative
molecular mass of a gas.
(e) Explain diffusion in terms of kinetic theory of matter.

This chapter focuses on the properties of matter in the gaseous state. The forces
of attraction between gas molecules are very weak. This allows gas particles to
be in continuous random motion because they posses kinetic energy. For this
reason gases spread to occupy any available space.
To explain the behaviour of gases, it is important to understand the
interrelationship between pressure, volume and temperature of a fixed mass of a
gas.
Gases play an important role in our daily lives. For instance, vehicle and
bicycle tyres, weather balloons and balls are filled with air.

Boyle’s Law
Boyle’s law deals with the relationship between pressure and volume of a fixed
mass of a gas when temperature is kept constant.
Experiment 1.1: How does the change in volume of a fixed mass of
gas affect its pressure if the temperature is kept constant?
Draw air into the barrel of a bicycle pump and close the outlet with the thumb as
shown in figure 1.1. With the outlet closed, push the piston slowly. Take note of
the force needed to keep the nozzle closed as the piston is pushed further into the
barrel. Observe the change in the volume of the gas during the experiment.
 Note:
This experiment can also be done using
a syringe.

Fig. 1.1: The Effect of change in volume on pressure of a fixed mass of gas

Answer the following questions

1. What happens to the volume of air as the piston is pushed in?
2. What change occurs in the pressure of the enclosed air as the piston is
pushed in?
3. How does the volume of the air change with pressure?
4. Explain the changes in 3 in terms of the kinetic theory.

Discussion
As the piston is pushed into the barrel the volume of the fixed mass of gas
reduces. At the same time the force needed to keep the gas in the barrel
increases. The gas exerts more pressure on the finger.
Pressure in a gas is as a result of the collisions of the gas molecules with the
walls of the container. When the volume of the fixed mass of a gas is decreased
through compression at constant temperature, the molecules travel a shorter
distance to collide with the walls of the container, leading to increased number of
collisions per unit time. The pressure of the gas therefore increases with the
increased rate of collisions. The increase in the force required to keep the nozzle
closed as the gas is compressed, is as a result of the increased gas pressure
inside.
The behaviour of a gas at constant temperature is summarised by Boyle’s
law: The volume of a given mass of a gas is inversely proportional to its
pressure at constant temperature.
What Boyle’s law implies is that as the pressure increases, the volume
decreases. Figure 1.2 illustrates this relationship.

Fig 1.2: Representation of variation of volume with pressure at constant temperature

Table 1.1 Shows sample results obtained from an experiment carried out to
investigate the relationship between the volume of a fixed mass of a gas with its
pressure at constant temperature.
Table: 1.1: Variation of volume and pressure in a fixed mass of gas

The pressure of the gas inside the barrel of the pump is directly proportional
to the physical pressure applied to compress the gas. A graph of the physical
volume is a curve as shown in figure 1.3.
Fig. 1.2: Graph of Pressure against Volume of a fixed mass of gas at constant temperature.

The mathematical expression of Boyle’s law is:

Hence, VP = Constant
The expression implies that when the volume of a fixed mass of a gas
changes from V1 to V2 its pressure also changes from P1 to P2. This leads to the
general expression:
P1V1 = P2V2.
Table 1.2: includes the values of
Table 1.2: Variations of volume and pressure in a fixed mass of gas 1/volume values.
Fig. 1: Graph of pressure of a fixed mass of a gas against the reciprocal of its volume at constant
temperature

When a graph of pressure of a fixed mass of gas is plotted against the reciprocal
of volume, a straight line is obtained. The SI unit of pressure is the Pascal (Pa).
It is equal to one Newton per square metre (NM-2). Other units used to express
pressure are atmospheres. One atmospheric pressure is equal to 760 mmHg
pressure or 1.01325 × 105 Pascals. The SI unit of volume is cubic metres (m3).
One cubic metre is equal to 1.0 × 106 cubic centimetres (cm3).
Worked Examples
1. A volume of 375 cm3 of a gas has a pressure of 20 atmospheres. What will
be its volume if pressure is reduced to 15 atmospheres?
Solution
 From Boyle’s law, P1 V1 = P2V2
P1 = 20 atmospheres, P2 = 15 atmospheres, V1 = 375 cm3, V2 = ?
Substituting for P1, V1 and P2 the equation becomes;

2. A given mass of gas occupies a volume of 200 cm3 at a pressure of 5

atmospheres. At what pressure will the gas have a volume of 800 cm3?
Solution
From Boyle’s law, P1V1 = P2V2
P1 = 5 atmospheres, P2 = ?, V1 = 200 cm3, V2 = 800 cm3
5 × 200 = P2 × 800

P2 = 1.25 atmospheres
3. A certain mass of gas occupies 250 cm3 at 25°C and 750 mmHg. Calculate
its volume at 25°C if pressure changes to 760 mmHg in SI Units.
Solution
V1 = 250 cm3, V1 = ?, P1 = 750 mmHg, P2 = 760 mmHg

4. At a Constant temperature, a gas at 540 mmHg pressure occupies a volume

of 300 litres. The gas is made to expand and occupy a volume of 600 litres.
What is the new gas pressure in SI Units?
P1 = 540 mmHg, V1 = 300 cm3, V2 = 600 cm3
 540 × 300 = P2 × 600

Exercise 1.1
1. A gas occupies 500 cm3 at a pressure of 760 mmHg. If the pressure is
doubled, what volume would the gas occupy?
2. The volume of a given mass of a gas at 25°C and 750 mmHg pressure is 456
cm3. What will the volume be at 25°C and 750 mmHg pressure?
3. Table 1.3 shows the relationship between the volume of a fixed mass of a
gas and its pressure at a constant temperature.
Table 1.3: Variation of volume against pressure in a fixed mass of gas at constant temperature

(a) Calculate the reciprocal of pressure to complete the table.

(b) Plot a graph of volume against the reciprocal of pressure.
(c) Use the graph to determine the volume of the gas at a pressure of 3.2
atmospheres.
(d) What is the relationship between the volume and the reciprocal of
pressure as illustrated by the graph?
4. Use the kinetic theory of matter to explain how a decrease in the volume of
a sample of a fixed mass of a gas affects its pressure at constant
temperature.
5. (a) State Boyle’s law and state the general mathematical expression based
 on the law.
(b) A gas occupies 55 cm3 at 774 mmHg pressure. Calculate the new
volume if the pressure is caused to change to 760 mmHg (express your
answer in SI units).
6. Would you expect a gas to obey Boyle’s Law at very high pressure,
temperature being kept constant? Give reasons for your answer.

Charles’ Law
Charles’ Law deals with the relationship between the volume of a fixed mass of
a gas with its temperature at constant pressure.

Experiment 1.2: How does the volume of a fixed mass of gas vary
with temperature at constant pressure?
Fit a narrow glass tube into a rubber bung. Loosely fix the bung in a round
bottomed flask. Introduce a drop of coloured water into the glass tube. When the
drop is half way down the glass tube, firmly stopper the flask making it airtight.
Note the position of the coloured water column in the tube. Immerse the flask in
a trough of warm water. Observe and record what happens to the water column.
Repeat the experiment using ice cold water in a trough. Record your
observations.

Fig 1.5: Volume of a given mass of a gas

Answer the following questions

1. What happens to the water column when the flask is warmed or cooled?
 2. How does the change in temperature affect the volume of the fixed mass of
gas?
3. Which factor is kept constant in this experiment?
4. Explain the observations made during the experiment in terms of the
kinetic theory.

Discussion
When the flask is immersed in a trough of warm water, the column of coloured
water first drops then moves up steadily.

Fig 1.6: Changes of volume with temperature

When the flask is immersed in warm water the coloured water column in the
capillary tube drops initially because the flask expands before the gas inside
absorbs heat to start expanding.
When the gas inside heats up, it expands and pushes up the water column in
the capillary tube. When a fixed mass of a gas is heated at constant pressure, its
volume increases to counter balance the constant pressure. The heat energy
increases the kinetic energy of the gas molecules. This leads to increased rate of
collisions with the walls of the container causing an increase in the gas pressure.
The relationship between temperature and volume of a fixed mass of gas is
summarised by Charles’s Law: The volume of a given mass of a gas is directly
proportional to its absolute temperature, its pressure being kept constant. The
law implies that the volume of a fixed mass of a gas increases in the same
proportion, as the absolute temperature provided its pressure remains constant.
Figure 1.7 illustrates this relationship.
Fig. 1.7: Variation of volume of a fixed mass of gas with absolute temperature at constant pressure

For the Michelin man, the challenge is to keep the volume constant!

Mathematically, Charles’s Law is expressed as;

Volume α absolute temperature. V α T
(Where V is the volume of the gas and T its absolute temperature in Kelvin).
Thus, = constant
When the volume of a fixed mass of a gas changes from V1 to V2, its absolute
temperature changes from T1 to T2 leading to the expression:
Table 1.4 gives sample results obtained from an experiment carried out to
investigate the relationship between the volume of a fixed mass of a gas and its
temperature at constant pressure.
Table 1.4: Sample results of volume of a fixed mass of a gas with its temperature

A graph of volume of a fixed mass of a gas against temperature is a straight line.

The graph intercepts the temperature axis at −273 °C when extrapolated as
shown in figure 1.8

Fig. 1.8: A graph of volume of a fixed mass of a gas against temperature at constant pressure.

A gas whose volume is theoretically zero at -273°C is referred to as an ideal

gas. In reality, a gas would have turned into a liquid before reaching a
temperature of −273°C.
The temperature at which the volume of a gas is assumed to be zero is called
absolute zero. From the absolute zero temperature, the absolute temperature
scale is derived. The lowest temperature on the absolute scale is zero Kelvin (0
K). The Kelvin (K) is the SI unit of the temperature on the absolute scale. The
equivalence of −273°C on the Kelvin scale is 0 K.
Temperature inter conversion from one scale to the other is done as follows:
1 To convert temperature in degrees Celsius (°C) to Kelvin (K), add 273. For
example, to convert 204 °C to Kelvin add 273 this;
T = 204 + 273
= 477K
2. To convert temperature in the Kelvin scale to degrees Celsius, subtract 273.
For example, convert 405 K to degrees celsius (°C)
t = 450 – 273
= 177°C.

Worked Examples
1. Convert the temperatures below to the absolute scale:
(i) 0°C
(ii) 25°C
(iii) –20°C
Solution
T = t + 273
(i) 0 + 273 = 273 K
(ii) 25 + 273 = 298 K
(iii) –20 + 273 = 253 K

Note:
Temperature on the Kelvin scale is
denoted by T, while on the celsius scale
it is denoted by t.

2. Convert the temperature recorded below in Kelvin to temperature in degrees

celsius (°C):
 (i) 0 K
(ii) 250 K
(iii) 273 K
Solution
t = T – 273
t = T – 273
t = T – 273
(i) 0 – 273 = – 273°C
(ii) 250 – 273 = – 23°C
(iii) 273 – 273 = 0°C

3. A gas occupies 450 cm3 at 27°C. What volume would the gas occupy at
177°C, if its pressure remains constant?
Solution
From Charles’s Law:
Converting the temperature to absolute temperature then substituting for V1,
T1 and T2 then:

4. At a temperature of 57°C, nitrogen gas occupies a volume of 750 cm3. At

what temperature will the gas occupy 100 cm3. Express the answer in
degrees celsius.
Solution
Exercise 1.2
1. What is the temperature on the Kelvin scale of each of the following?
(a) 100°C
(b) –100°C
(c) 22°C
2. What is the temperature in celcius of each of the following?
(a) 303 K
(b) 400 K
(c) 0 K

3. A gas occupies 200 cm3 at 0°C and 740 mmHg pressure. What volume will
it occupy at 47°C at the same pressure?
4. A balloon contains 100 cm3 of air at 25°C. The balloon was put outside in
the sun where the temperature was 40°C. Calculate the new volume of the
air.
5. The following diagram represents a set up used to investigate the
relationship between the volume of a fixed mass of gas with its temperature.
The atmospheric pressure was 0.8 atmospheres.
(a) What is the initial gas pressure?
(b) State and explain the observation made when:
(i) The flask is held between the palms of the hand.
(ii) The flask is immersed in water at a temperature below the room
temperature.
6. (a) State Charles’s Law.
(b) Draw a sketch graph to illustrate Charles’s Law.

Combined Gas Law

The combined gas law deals with the variation in the volume of a fixed mass of a
gas with respect to changes in temperature and pressure. The mathematical
expression of Charles’s Law, V α T can be combined with that of Boyle’s law V
α to obtain the expression:

Therefore, PV α T
Hence, = Constant
If a fixed mass of a gas of volume V1 exerts a pressure P1 at absolute
temperature T1, the expression may be written as:

Suppose the same mass of gas has a volume, V2, and exerts a pressure, P2, at
absolute temperature, T2, then the expression becomes:

Therefore,
This is an important equation. It enables the volume of a gas to be obtained
under any conditions of temperature and pressure provided its volume under
some other conditions of temperature and pressure is known. It is called the
ideal gas equation.

Standard Conditions
Both temperature and pressure changes in a gas can cause the volume to change.
For this reason, volumes of gases are always compared under the same
conditions of temperature and pressure.

There are two conditions considered when comparing volumes of gases:

1. Standard temperature and pressure (s.t.p). The s.t.p conditions refer to a
temperature of 273 K and a pressure of 760 mmHg (1 atmosphere).
2. Room temperature and pressure (r.t.p). This refers to a temperature of 298 K
and a pressure of 760 mmHg.
It should be seen that from the standard conditions, all computations of
temperature should be expressed in Kelvin.

Worked Examples
1. What will be the volume of a given mass of oxygen at 25°C if it occupies
100 cm3 at 15°C? (pressure remains constant).
Solution
Let the initial volume, temperature and pressure be V1, T1, P1 respectively,
and the final be V2, T2, P2. From the gas equation;

Where, V1 = 100 cm3, T1 = 15 + 273 = 288K and P1 = P2 = constant.

2. A given mass of a gas occupies 20 cm3 at 25°C and 670 mmHg pressure.
Find out the volume it will occupy at:
(a) 10°C and 335 mmHg
(b) 0°C and 760 mmHg
 Solution
(a) From the gas equation,

Where, P1 = 670 mmHg, V1 = 20 cm3,

T1 =25 + 273 = 298 K, T2 = 10 + 273 = 283 K, P2 = 335 mmHg, V2 = ?

Some Applications of Gas Laws

The effects of changes in pressure, volume and temperature on a fixed mass of a
gas have been used in a wide range of applications which include:
1. Inflating tyres, balls and balloons appropriately depending on the prevailing
temperature conditions.
2. Designing of aerosol cans and tear-gas canisters which contain a gas
compressed under pressure to act as a propellant of liquid contents in the
cans.
3. Regulation of pressure in an aircraft for comfortable in flight environment at
high altitude.
Airliners have to undergo regular inspections for fuselage integrity

Exercise 1.3
1. At 27°C and 740 mmHg pressure, a sample of nitrogen gas occupies 30 cm3.
What will its volume be at s.t.p?
2. A given mass of a gas occupies 40 cm3 at 0°C and 680 mmHg pressure.
Determine the volume the gas would occupy at:
(a) –23°C and 760 mmHg pressure.
(b) 0°C and 380 mmHg pressure.
(c) r.t.p.
3. A fixed mass of a gas occupies 100 cm3 at −15 °C and 650 mmHg pressure.
At what temperature will it have a volume of 150 cm3 if the pressure is
adjusted to 680 mmHg?
4. Hydrogen gas in a 360 cm3 glass bulb at s.t.p is carefully transferred into
another glass bulb of volume 320 cm3 at a temperature of 51°C. Calculate
its new pressure.
5. A gas at −273°C is considered to be an ideal gas. Explain.
6. Draw a sketch of a graph illustrating the relationship between the volume of
a fixed mass of a gas and its absolute temperature at a constant pressure.
Diffusion and the Graham’s Law
Inter–molecular forces of attraction in gases are very weak because the inter-
molecular distances are large. A gas therefore, always spreads out to fill up all
the space available. This explains why the scent of a strong perfume reaches all
corners of a room as soon as the container is opened. The perfume spreads from
an area of high concentration to areas where its concentration is low. Diffusion
is the process by which particles spread out from a region of high concentration
to regions of low concentration. This section of the chapter examines diffusion in
liquids and gases and the factors affecting diffusion in gases.

Experiment 1.5: How does diffusion take place in liquids and gases?
Carry out the following experiments and record your observations in the table.
Table 1.5: Diffusion of solids in liquids
 Experiment Observation
(a) Half fill a beaker with clean water. Using a straw,
introduce a crystal of potassium manganate(VII) into the
water as in figure 1.10. Leave the set up undisturbed and
record the observation after:
(i) 40 minutes.
(ii) One day.
(b) Place four drops of liquid bromine in a gas jar. Invert an
empty gas jar over the jar containing bromine liquid as in
figure 1.11 (a) and (b). Leave undisturbed for 30 minutes.
(c) Place a piece of moist red litmus paper at the end of a
combustion tube. Soak cotton wool in concentrated
ammonia solution. Place the cotton wool at the other end
of the combustion tube as shown in figure 1.12.

Answer the following question

State and explain the observations made in the three experimental set ups.

Discussion
Experiment (a) shows that a solid placed at one point in liquid is capable of
spreading out to other parts of the liquid. The substance must have broken up
into smaller particles to be able to spread in the observed fashion. The spreading
out of the purple colour of potassium manganate(VII) on dissolving in water is
evidence for the movement of solute particles in a solvent.
The movement of potassium manganate(VII) particles in water is due to
collisions between potassium manganate(VII) particles and the water particles.
This is because they have kinetic energy.
Fig. 1.9: (a) Diffusion of a solid in a liquid.

Experiments (b) and (c) show that gaseous substances are able to spread out
from one area to another. Bromine vapour spreads and fills the two gas jars as
shown in figure. 1.10 (i) and (ii). This is evidence of movement of gas particles
through a gas medium.

Fig 1.10: (b) Diffusion in gases (air).

In figure 1.11, the wet red litmus paper turns blue indicating that the ammonia
molecules have spread along the combustion tube. This is evidence of movement
of gas particles in a gas.

Fig. 1.11:(c) Diffusion of a gas in air.

The spreading out of gas particles in air takes a shorter time than solid particles
in a solvent. This is because gas particles are far apart and have more kinetic
energy than the liquid particles.
Experiment 1.4: Do all gases diffuse at the same rate?
Clamp a glass tube (combustion tube 25 cm long) horizontally as shown in
figure 1.12. Soak one piece of cotton wool in concentrated ammonia and another
piece in concentrated hydrochloric acid. Insert them simultaneously at the
opposite ends of the glass tube and stopper both ends. Immediately start a
stopwatch and record the time taken for a change to occur in the glass tube.
Using a felt pen, mark on the tube where the change occurs. Measure the
distance covered by each gas. Record the distances as in table 1.6.

Fig. 1.12: Rate of diffusion of ammonia and hydrogen chloride in air

Table 1.6: Rate of diffusion of Ammonia and Hydrogen chloride in air.

Time taken for the change to occur (sec.)

Distance covered by ammonia gas (cm3)

Distance covered by hydrogen chloride gas (cm3)

Answer the following questions

1. What observations are made in the glass tube and after how long?
2. Which gas covered a longer distance?
3. Explain the observations made in the glass tube.
4. Determine the molecular masses of ammonia (NH3) and hydrogen chloride
(HCI). N = 14.0, H = 1.0, CI = 35.5.
5. Calculate the rate of diffusion of:
(a) Ammonia gas.
 (b) Hydrogen chloride gas.
6. What is the relative rate of diffusion of ammonia to hydrogen chloride gas
in air?

Discussion
Concentrated ammonia solution generates ammonia gas while concentrated
hydrochloric acid generates hydrogen chloride gas. Ammonia and hydrogen
chloride gases diffuse in air in the tube, and when their molecules meet, they
react to form white, solid ammonium chloride.
NH3(g) + HCl(g) NH4Cl(s)
During the experiment it was observed that ammonia gas whose molecular
mass is 17 g covered a longer distance before meeting with the hydrogen
chloride molecules whose molecular mass is 36.5 g. Table 1.7: Gives sample
results of a similar experiment.
Table 1.7: Sample results for the diffusion of ammonia and hydrogen chloride in air.

From the sample results; the rates of diffusion of the gases can be worked out
as follows:
In the experiment, the distance covered by ammonia was 12 cm while the
distance covered by hydrogen chloride was 8 cm within the same time interval
of 5 minutes. Using the data collected for the distance and time, the rate of
diffusion of ammonia gas in air is cm/minute and the rate of
diffusion of hydrogen chloride gas in air is cm/minute.
The relative rate of diffusion of ammonia gas compared to hydrogen chloride
gas in air is:

This means ammonia diffuses 1.5 times faster than hydrogen chloride.
The behaviour of gases when they diffuse is summarised by Graham’s Law:
Under the same conditions of temperature and pressure, the rate of diffusion of a
gas is inversely proportional to the square root of its density. The mathematical
expression of Graham’s Law is:

Meaning that:

When the rates of diffusion of two gases A and B are compared, the
equations are:

Since density is directly proportional to molecular mass, Graham’s law can also
be expressed as:
Therefore, if the rate of diffusion of two gases A and B are compared, then:

Where MA and MB are relative molecular masses of the gases A and B

respectively. Since Rate is inversely proportional to time, (Rate α ). It means
that it is also possible to compare the time taken for equal volumes of two gases
to diffuse under similar conditions:

This means that:

RATA = Constant, and RBTB = Constant
(R = rate, T = time)
Therefore,
RATA = RBTB and

Note:
The relative molecular mass of a
substance is equal to the sum of the
relative atomic masses of the constituent
elements in a compound.

Where TA and TB are the times of diffusion of gases A and B respectively.

Applying the equation above in the case of ammonia and hydrogen chloride
gases in experiment 1.4.
 Ammonia gas therefore diffuses 1.5 times faster than hydrogen chloride gas
under the same conditions of temperature and pressure. This is because ammonia
gas is less dense than hydrogen chloride gas. Therefore, gases with low densities
diffuse faster than those with high densities.
Worked Examples
1. Equal volumes of carbon(II) oxide and carbon(IV) oxide are allowed to
diffuse through the same medium. Calculate the relative rate of diffusion of
carbon(II) oxide. (C = 12.0, Oxygen = 16.0)
Solution
Relative molecular mass (Mr) of CO = 12 + 16 = 28
Relative molecular mass (Mr) of CO2 = 12 + 32 = 44

Carbon(II) oxide diffuses 1.254 times faster than carbon(IV) oxide.

2. If it takes 20 seconds for 200 cm3 of oxygen gas to diffuse across a porous
plug. How long will it take an equal volume of sulphur(IV) oxide to diffuse
across the same plug? (O = 16.0, S = 32.0).
Solution
3. Determine the molecular mass of the gas Y which diffuses times slower
than Oxygen. 0 = 16.0

4. If it takes 30 seconds for 100 cm3 of carbon(IV) oxide to diffuse across a

porous plate. How long will it take 150 cm3 of nitrogen(IV) oxide to diffuse
across the same plate under similar conditions? (C = 12.0, N = 14.0, O =
16.0).
Solution

Therefore, time taken for NO2 to diffuse is:

Alternative Working
Since equal volumes must be compared:
100 cm3 of CO2 takes 30 seconds

5. Calculate the relative rate of diffusion of ammonia gas compared to that

hydrogen chloride gas under the same conditions of temperature and
pressure.
From the expression:

This ratio implies that ammonia diffuses 1.5 times faster than hydrogen chloride
gas.
Summary
1. The pressure of a gas is the result of collisions between the gas particles and
the walls of the container.
2. When a gas is heated, the velocity of its particles increases since more
energy is supplied to them. Consequently, the frequency of gas particle
collisions with the walls of the container is raised leading to a rise in
pressure.
3. Boyle’s law states that: The volume of a fixed mass of gas is inversely
proportional to its pressure at constant temperature.
4. Charles’s law states that: The volume of a fixed mass of gas is directly
 proportional to its absolute temperature at constant pressure.
5. The relationship between volume, pressure and temperature of a fixed mass
of gas can be given by the expression which combines both Charles’s and
Boyle’s laws and is known as the Combined Gas Law (Ideal Gas
Equation) = constant.
6. Absolute temperature (absolute zero) is the temperature at which the
volume of an ideal gas is assumed to be zero.
7. Standard temperature and pressure, denoted as s.t.p. refers to a temperature
of 0°C (273 K) and a pressure of 760 mmHg (1 atmosphere).
8. The initials, r.t.p, refer to room temperature and pressure. By definition, it
specifies a temperature of 25°C (298 K) and a pressure of 760 mmHg (1
atmosphere)
9. One atmospheric pressure = 760 mmHg = 1.0132 × 105 Pascals (Pa).

Revision Exercise
1. A glass syringe contains 80 cm3 of air at 38°C and 2 atmospheres pressure.
Calculate the volume of air in the syringe at a temperature of 38°C and 4
atmospheres.
2. In an experiment, 375 cm3 of gas P have a pressure of 800 mmHg. What
will be the volume if pressure is reduced to 720 mmHg pressure?
(Temperature kept constant).
3. A fixed mass of a certain gas has a volume of 96 cm3 at 67°C and 700
mmHg pressure. Find the volume the gas would occupy at s.t.p.
4. A certain volume of oxygen diffused from a given apparatus in 125 seconds.
In the same conditions, the same volume of gas N, diffused in 100 seconds.
Calculate the relative molecular mass of N. (O = 16.0).
5. Two gases X and Y have relative densities of 1.98 and 2.90 respectively.
They diffuse under the same conditions.
(a) How do their rates of diffusion compare?
(b) Determine the relative molecular mass of X, given that the relative
molecular mass of Y is 64.
6. Hydrogen diffuses seven times faster than gas X under the same conditions
of temperature and pressure. Calculate the relative molecular mass of gas X
if that of hydrogen is 2.
 7. A volume of 120 cm3 of nitrogen gas diffused through a membrane in 40
seconds, how long will 240 cm3 of carbon(IV) oxide defuse through the
same membrane?
8. In a experiment, 60 cm3 of oxygen diffused through a porous pot in 10
seconds and 100 cm3 of chlorine diffused through the same porous pot in 30
seconds. If the density of oxygen is 1.25 g/cm3, calculate the density of
chlorine.
9. Explain why motor vehicle tyres should not be inflated hard during the dry
season if the vehicle is to be driven over a long distance during the day.
10. Use the kinetic theory to explain why the pressure of a fixed mass of a gas at
constant temperature increases when the volume of its container is
decreased.
 Chapter The Mole
2

By the end of this topic, the learner should be able to:

(a) Define the mole and relate it to relative atomic mass.

(b) Convert mass into moles, and moles to mass.
(c) Use data to determine the empirical and molecular formulae of
compounds.
(d) Define the terms concentration, molarity and dilution of a solution.
(e) Define and prepare molar solutions.
(f) Carry out titrations and solve problems involving molar solutions.
(g) Write full formulae and ionic equations.
(h) Define molar gas volume and atomicity of gases.
(i) State Avogadros’ and Gay Lussac’s laws and carry out related
calculations.
(j) Carry out calculations on molar gas volumes both at standard temperature
and pressure and room temperature and pressure.

Chemical reactions involve atoms, molecules or ions. The masses of individual

atoms and molecules are very small. For example, the mass of an atom is in the
order of 10-22g. Therefore, the masses used during experiments contain large
numbers of elementary particles.
When dealing with a large number of objects, it is convenient to use a
suitable “counting unit”. For example, a pair represents two objects and a dozen
represents twelve objects. These are examples of ‘counting units’. The table
below shows various types of fruits and their masses.

Fruit Mass (g)

Banana 100
Orange 200
 Mango 300

Assuming that fruits of the same type have the same mass, the mass of:
(a) A dozen bananas equals 1200 g.
(b) A dozen oranges equals 2400 g.
(c) A dozen mangoes equals 3600 g.
It will be noticed that a dozen of each type of fruit has a different mass even
though the number of units remains twelve. Thus, different masses are required
to obtain the same number of fruits. This example shows that weighing can be
used as a means of counting.
In order to establish a “counting unit”, chemists have found it convenient to
express the sum of any atom relative to that of a chosen atom of a particular
element. It is therefore, possible to estimate the number of atoms, molecules or
any other particle by weighing.

Fruits arrive at grocers after bulk orders!

Relative Mass
Experiment 2.1: How many times is a large nail heavier than a
smaller one?
Take six different sizes of nails (2.5 cm to 15.0 cm long). Using a beam balance,
find out how many 2.5 cm nails are needed to balance one 15 cm nail. Record
your results as in table 2.1. Repeat the experiment using 12.5 cm, 10.0 cm, 7.5
cm, 5.0 cm and 2.5 cm nails in place of the 15.0 cm nail.
Table 2.1:Counting by weighing
 Answer the following questions
1. Which nail size was taken as the standard reference in this experiment?
2. Explain what is meant by the term relative mass.
3. What are the units for the relative mass in this experiment?
4. What are the main sources of error in this experiment?

Discussion
Relative mass in this experiment is the mass of the big nail compared to the
smallest. The smallest nail is taken as the reference because the ratios obtained
would be whole numbers. If five small nails balance one big nail then the
relative mass of the big nail is five. See table 2.2.
Table 2.2: The idea of relative mass

In this experiment, it is assumed that all nails of the same size have equal
masses.
The idea is used in Chemistry with carbon-12 as the reference. When the
mass of any atom is compared to that of another, it is referred to as relative
atomic mass. Originally, hydrogen was chosen as the reference scale because it
was the lightest element. The mass of a hydrogen atom was given an arbitrary
value of one atomic mass unit (1 a.m.u.). The masses of all other atoms were
then measured relative to hydrogen as follows:
 On this scale, for example, the sodium atom is 23 times heavier than the
mass of a hydrogen atom. Therefore, the relative atomic mass of sodium is 23.
In the early twentieth century, the hydrogen scale was replaced by the
oxygen scale. It was later discovered that the oxygen scale led to problems due
to the existence of oxygen isotopes. Therefore, in 1961, the International Union
of Pure and Applied Chemistry (IUPAC) recommended a new scale based on
Carbon –12 isotope. Carbon-12 was chosen as the reference because it is a stable
solid and a very common element.
On this scale, an atom of carbon is assigned a value of exactly 12.00 atomic
mass units (12.00 a.m.u). Today, the relative atomic mass of an element is
defined as:

Since relative atomic mass is a ratio, it has no units. Table 2.3 shows the relative
atomic masses of some elements.
Table 2.3: Relative Atomic masses of some selected elements

Experiment 2.2: How many nails of each size have a mass equal to
the corresponding relative mass expressed in grams?
Using a beam balance, find out the number of 2.5 cm nails that would balance a
mass of one (1) gram. Repeat the experiment using 5 cm, 7.5 cm, 10.0 cm, 12.5
cm and 15.0 cm with the corresponding relative masses. Record your results in
table 2.4.
Table 2.4: The counting unit
Discussion
It will be noticed that the number of nails of each size with a mass in grams
equal to the corresponding relative mass is always a constant. Thus, there is a
constant number associated with the relative mass of each size.
In Chemistry, it has been established that one relative atomic mass unit in
grams of any element contains the same number of atoms.
To obtain the same number of atoms, different masses have to be weighed.
This is because individual atoms of different elements have different masses.
One gram of hydrogen contains the same number of atoms as 24 g of
magnesium.
The number of atoms in one relative atomic mass unit in grams of any
element has been established to be 6.023 × 1023. This number is referred to as
Avogadro’s Constant, 'L'. The amount of any substance that contains
Avogadro’s number of particles is called a mole.
Just as a dozen contains twelve items, a mole contains 6.023 × 1023 particles.
The unit “Mole” is used to measure the amount of particles (atoms, molecules,
ions, electrons etc.) of any substance. The mass in grams of one mole of a
substance is referred to as molar mass.

Exercise 2.1
1. Copy and complete the following table
2. How many atoms are there in one mole of oxygen atoms?
3. What mass of oxygen atoms would you expect to contain the same number
of atoms as six grams of carbon?
4. How many atoms are there in 20 g of calcium?
5. Calculate the mass in the following atoms:
(i) 3.0115 × 1023 atoms of aluminium (A1 = 27.0).
(ii) 12.046 × 1023 atoms of iron (Fe = 56.0).
Inter Conversion of Molecules and Moles
Some elements do not exist as atoms but as molecules. For example, a sample of
oxygen gas is made up of oxygen molecules, O2. This is because oxygen atoms
cannot exist freely on their own.
There are two atoms of oxygen in one molecule of oxygen. Therefore, the
relative molecular mass of oxygen molecule is, 16 × 2 = 32. This implies that a
mole of oxygen molecules has a mass of 32 g. This mass contains 6.023 × 1023
molecules of oxygen.
Since each molecule of oxygen has two atoms, then 1 mole of oxygen
molecules would contain 2 × 6.023 × 1023 = 1.2046 × 1024 atoms of oxygen.
Similarly, 0.5 mole of oxygen molecules would contain: 6.023 × 1023 × 0.5 =
3.0115 × 1023 molecules of oxygen and 3.0115 × 1023 × 2 = 6.023 × 1023 atoms
of oxygen.

Exercise 2.2
1. Name other elements which exist as molecules.
2. How many chlorine atoms are there in 1 mole of chlorine molecules?
3. What mass in grams will contain 1 mole of hydrogen molecules?
4. How many atoms of bromine are there in two moles of bromine gas?
5. (a) Calculate the number of molecules of nitrogen that are in 0.5 moles of
nitrogen atoms.
(b) Calculate the number of molecules in 2.5 moles of nitrogen gas.
6. Calculate the number of moles in the following molecules:
(i) 1.2046 × 1024 molecules of oxygen.
(i) 9.0345 × 1023 molecules of ammonia.
Inter conversion of Mass and Moles
(i) Relationship between mass of an element and the mole.
It has already been shown that one mole of an element has a mass equal to its
relative atomic mass in grams. Therefore, one mole of magnesium has a mass of
24 g. What is the mass of 0.5 mol of magnesium?

But, 24 g/mol is the molar mass of magnesium.

Therefore, it can be deduced that:
Mass of an element (in grams) = Molar mass × number of moles.
Worked Examples
1. Calculate the mass of 0.4 moles of calcium (Ca = 40).
Mass = molar mass × number of moles
= 0.4 × 40
= 16 g
2. Determine the number of moles in 13.5 g of aluminium (A1 = 27)
27 g = 1 mole
This formula can easily be remembered by using the triangle below:

Key: • Horizontal line in triangle represents division sign.

• Vertical line in triangle represents multiplication sign.
Therefore, it would be seen that:

Exercise 2.3
(i) How many moles are there in 3 g of carbon?
(ii) How many moles are there in 4.6 g of sodium?
(iii) Calculate the mass of 0.25 moles of Beryllium.
(iv) Calculate the molar mass of an element if a mass of 5.6 g contains 0.1
moles of the element. (Na = 23, Be = 9, C = 12)

(ii) Relationship Between Relative Molecular Mass and the Mole

Relative molecular mass of an element or compound is the sum of all the relative
atomic masses of the atoms in a molecule of the element or compound. For
example, the relative molecular mass of chlorine Cl2 is 35.5 × 2 = 71, while that
of water, H2O is (1×2) + 16 = 18. The molar mass of chlorine is therefore 71
g/mol and that of water 18 g/mol.
For ionic compounds, the term relative formula mass is used. Relative
formula mass is the sum of the relative atomic masses of all the atoms in a
formula unit of a compound. For example, the relative formula mass of
potassium sulphate K2SO4 is (39 × 2) + 32 + (16 × 4) = 174. The molar mass of
potassium sulphate is 174 g/mol.
It is important to note that one mole of any substance has a mass equal to the
relative formula mass of that substance. The substance could be made of atoms,
ions or molecules.

Exercise 2.4
1. Copy and complete the following table:

Name of compound Formula Molecular/Formula mass

Carbon(IV) oxide

Hydrochloric acid

Sodium carbonate

Calcium chloride

Sulphur(IV) oxide

Ammonium sulphate

Ammonia

2. How many moles are there in 10.6 g of sodium carbonate?

3. What is the mass of 0.2 moles of ethanol, C2H5OH?
4. How many moles of oxygen atoms are there in one mole of copper(II)
sulphate?
5. What percentage by mass of sodium is there in one mole of sodium nitrate,
NaNO3?

Empirical and Molecular Formula

Quantitative chemical analysis gives information about proportion by mass of
the elements making-up a compound. If the elements present in a compound are
known, their relative atomic masses can be used to calculate the amounts of the
elements which react together or the products formed. Once the proportions by
mass of the elements are established, the chemical formula of the compound can
be determined.
Empirical Formula
The empirical formula of a compound shows the simplest whole number ratio in
which atoms combine to form the compound. The formula is determined from
experimental data. It provides useful information about the chemical formula of
a compound.
Experiment 2.3: What is the formula of the compound formed when
magnesium burns in air?
Weigh a clean dry crucible together with its lid. Clean about 15 cm length of
magnesium ribbon thoroughly. Using a pencil, wind the magnesium ribbon into
a coil. Place it inside the crucible and replace the lid. Weigh again the crucible
together with the magnesium ribbon and lid. Heat the contents strongly as in
figure 2.1 for a few minutes, occasionally lifting the lid slightly using a pair of
tongs.

Fig. 2.1: Oxidation of magnesium.

When there are no more flare-ups, remove the lid and heat the crucible strongly.
Remove the source of heat and allow the crucible to cool. When cold, replace the
lid and weigh again.
Repeat the heating and cooling until a constant mass is obtained. Record your
results as in table 2.7.
Table 2.7: Experimental results

Mass of empty crucible + lid

Mass of crucible + lid + magnesium

 Mass of crucible + magnesium oxide + lid

Mass of magnesium

Mass of magnesium oxide

Mass of oxygen

Answer the following questions

1. Why is it necessary to clean the magnesium ribbon?
2. Why was the lid kept on the crucible at first?
3. What was the purpose of the occasional lifting of the lid?
4. Explain why it is necessary to heat the crucible and its contents until there
is no further change in mass.
5. What masses of magnesium and oxygen combine to form magnesium
oxide?
6. How many moles of atoms of each element reacted in this experiment?
7. Calculate the mole ratio of magnesium to oxygen in magnesium oxide.
8. What is the simplest formula of magnesium oxide?
9. State the possible sources of error in this experiment.

Discussion
When a piece of magnesium burns in air, it combines with oxygen to form
magnesium oxide. The magnesium ribbon is cleaned at the start of the
experiment so as to remove any oxide film on it. The products weigh more due
to the oxygen which combines with the magnesium. The mass of the magnesium
used and the mass of the magnesium oxide formed can be obtained from the
results.
When carrying out the experiment, it is important to keep the lid in place to
prevent any solid from escaping. It is also necessary to lift the lid from time to
time to allow in air. The purpose of heating until a constant mass is obtained
ensures that all the magnesium has reacted.
The number of moles of atoms of magnesium, and oxygen which combine
can be found by dividing the reacting masses of these elements by their
respective relative atomic masses. Sample results from an experiment are as
shown in table 2.8.
Table 2.8: Sample experimental data used in obtaining the formula of magnesium oxide

Mass of empty crucible + lid, (A) 19.52 g

Mass of crucible + lid + magnesium, (B) 20.36 g

Mass of crucible + lid + magnesium oxide, (C) 20.92 g

Mass of magnesium, (D) = (B – A) 0.84 g

Mass of magnesium oxide, (E) (C – A) 1.40 g

Mass of oxygen, (F = E – D) 0.56 g

The formula of magnesium oxide can now be determined as follows:

Reacting elements: Magnesium Oxygen

Reacting masses (g): 0.84 0.56
Relative atomic mass: 24 16
No of moles =
Mole ratio 0.35 0.35
(divide by the smallest) 1 : 1

Note:
Any variation from this ratio is due to
experimental errors and side reaction
such as the formation of magnesium
nitride.

It follows that, one mole of magnesium atoms combines with one mole of
oxygen atoms. Therefore, the simplest formula of magnesium oxide is MgO. In
this case, it also happens to be the chemical formula.
Experiment 2.4: What is the formula of the compound formed when
copper combines with oxygen?.
Weigh an empty porcelain boat. Place a small amount of copper(II) oxide into
the porcelain boat and weigh again. Place the porcelain boat and its contents in a
combustion tube as shown in figure 2.2. Pass a stream of laboratory gas through
the tube for a short time. Light the gas at the end.

Fig. 2.2: Reduction of copper(II) oxide.

Start to heat the copper(II) oxide and record your observations. Continue
heating the tube until there is no further change. Remove the source of heat but
keep the lab gas flowing. When the tube has cooled, turn off the gas supply.
Carefully remove the porcelain boat with the residue from the combustion tube
and weigh. Repeat the procedure until a constant mass is obtained. Record the
results as in table 2.9.
Table 2.9: Experimental results for the reduction of copper(II) oxide

Mass of empty porcelain boat

Mass of porcelain boat + copper(II) oxide

Mass of porcelain boat + residue

Mass of copper(II) oxide

Mass of copper

Mass of oxygen
 Answer the following questions
1. Why is it necessary to ensure that all the air in the combustion tube is
driven out before heating?
2. How would you know that the reaction is complete?
3. What is the colour of the residue?
4. Explain why it is necessary to keep the stream of lab gas on as the product
is cooling.
5. What other reducing agents can be used to remove oxygen from copper(II)
oxide? Explain why some of these agents could not be used in this
experiment.
6. Determine the formula of the copper oxide from these results.
7. Name the possible sources of error in this experiment.
8. Find the percentage by mass of copper and oxygen in copper(II) oxide.

Discussion
The empirical formula is determined indirectly by breaking down copper(II)
oxide into copper and oxygen, using a suitable reducing agent. In this
experiment, black copper(II) oxide is reduced to reddish brown metallic copper
using hydrogen gas. The oxygen combines with lab gas to form water and
carbon(IV) oxide.
Before heating, lab gas was passed through the tube to remove any traces of
air in the tube. Metallic copper was cooled in a stream of lab gas to prevent re-
oxidation of the hot metal by air. Ammonia gas can be used as the reducing
agent in place of lab gas. Other reducing agents such as carbon and metals that
are more reactive than copper can also be used to remove oxygen from
copper(II) oxide but they are normally not used because it would be difficult to
isolate the copper. The results of a similar experiment are given in table 2.10.
Table 2.10: Sample results of the reduction of copper(II) oxide

Mass of empty porcelain boat, (A) 15.6 g

Mass of porcelain boat + copper(II) oxide, (B) 19.1 g

Mass of porcelain boat + residue, (C) 18.4 g

Mass of copper(II) oxide, (D) = (B – A) 3.5 g

 Mass of copper, (E) = (C – A) 2.8 g

Mass of oxygen, (F) = (D – E) 0.7 g

The formula can now be determined as follows:

Element Copper Oxygen

Mass: 2.8 g 0.7 g
Relative atomic mass: 63.5 16
No. of moles:
Mole ratio 1 : 1

One mole of copper combines with one mole of oxygen. The simplest
formula is CuO. This is also the chemical formula of copper(II) oxide.
Chemical formula is also derived from percentage composition of the
constituent elements. Using the data from table 2.10 for copper(II) oxide
experiment,

The percentages are then taken to represent the actual masses of the elements
in the compound.
The empirical formula is then determined as follows:

Element Copper Oxygen

Percentage composition: 80 20
Relative atomic mass: 63.5 16
No. of moles:
= 1.25 = 1.25
Mole ratio: 1 : 1

The empirical formula is CuO.

Worked Example 1
An oxide of silicon was found to contain 47% by mass silicon. What is the
empirical formula of the oxide? (Si = 28, O = 16).
Solution

Element Silicon (Si) Oxygen (O)

Percentage composition: 47 100 – 47 = 53
Relative atomic mass: 8 16

Mole ratio: :
=1 : = 1.94
Simple whole No. ratio 1 : 2

Therefore, the empirical formula of silicon oxide is SiO2.

Worked Example 2
The percentage composition by mass of an oxide of iron is 70% iron and 30%
oxygen. Determine its empirical formula. (Fe = 56, O = 16).
Solution

Element Iron(Fe) Oxygen(O)

Composition %: 70 30
Relative atomic mass: 56 16
No. of moles:

Mole ratio: 1 : 1.5

To make it a whole number, ratio multiply by 2

 2 : 3
The empirical formula of the iron oxide is Fe2 O3.

Exercise 2.5
1. A compound weighing 42 grams was found to contain 12 grams magnesium,
6 grams carbon and the rest oxygen. Determine the empirical formula of the
compound. (Mg = 24.0, C = 12.0, O = 16.0).
2. A sample of a hydrocarbon of mass 51.2 g was analysed and found to
contain 12.8 grams hydrogen. If the formula of the hydrocarbon is Cx Hy.
Find the values of x and y. (C = 12.0, H = 1.0).
3. The empirical formula of an organic compound is C1H2 O1. If the empirical
formula mass of the compound is 30. Find the percentage composition of
the elements in the compound (C = 12.0, H = 1.0, O =16.0).
4. A 9.6 gram piece of clean magnesium burned completely in 6.4 grams of
pure oxygen, and the product was allowed to cool to room temperature and
pressure r.t.p. Determine the reaction mole ratio, and hence the formula of
the oxide. (Mg = 24.0, O = 16.0).
5. A sample of anhydrous copper(II) sulphate on analysis was found to contain
6.4 grams of copper, 3.2 grams sulphur and 6.4 grams oxygen. Determine its
empirical formula. (Cu = 64.0, S = 32.0, O = 16.0).
6. In an experiment 3.10 grams of a compound of carbon, hydrogen and
oxygen produced 4.4 grams of carbon(IV) oxide and 2.7g of water on
complete combustion. Determine the empirical formula of the compound.
(C = 12.0, O = 16.0, H = 1.0).
Molecular Formula
For ionic compounds, the empirical formula is the same as the chemical formula.
For molecular compounds, the empirical formula may not be the same as the
molecular formula.
Molecular formula shows the actual number of each kind of atoms present in
a molecule of the compound. If the empirical formula is known, then the
molecular formula can be determined by the relationship.
(Mass of empirical formula)n = Molecular mass,
Where n is a whole number.
The molecular mass is always a multiple of the empirical formula mass.
Worked Example 1
A hydrocarbon was found to contain 92.3% carbon, and the remaining is
hydrogen. If its molecular mass is 78, determine its molecular formula. (C = 12,
H = 1).
Solution

Element Carbon(C) Hydrogen(H)

Percentage composition: 92.3 7.7
R.A.M: 12 1
No. of moles:
= 7.7 : = 7.7
Mole ratio: 1 : 1

The empirical formula is CH.

Therefore, the molecular formula is C6H6

Worked Example 2
A compound of carbon, hydrogen and oxygen contains 54.55% carbon, 9.0%
hydrogen, and 36.6% oxygen. If its relative molecular mass is 88, what is its
molecular formula? (C = 12, O = 16, H = 1).
Solution
First obtain the empirical formula as follows:
The simplest formula is C2H4O.
Since the molecular mass is 88, then

The molecular formula is C4H8O2.

Worked Example 3
When a certain hydrocarbon is burnt completely in excess oxygen, 5.28 g of
carbon (IV) oxide and 2.16 g of water were formed. If the molecular mass of the
hydrocarbon is 84, determine the molecular formula of the hydrocarbon.
Solution
This is an example where the mole ratio of the products can be used to determine
the formula of the reactant.

Products: CO2 H20

Mass: 5.28 2.16
Formula mass: 44 18
No. of moles:
Mole ratio: 1 : 1

Therefore, it implies that only one mole of the carbon(VI) oxide and one mole of
water were produced.
 The empirical formula is obtained by working out the masses of carbon and
hydrogen in carbon(IV) oxide and water respectively.

Products: Carbon Water (H2O)

(CO2)
Mass:
No. of moles:
Mole ratio: :
1 : 1

Therefore, the empirical formula is CH2.

Since the molecular mass is 84, then
(CH2)n = 84
(12 + 2)n =84
14n = 84
n =6
The molecular formula of the hydrocarbon, is C6H12.

Exercise 2.6
1. An organic compound has a relative formula mass of 90 grams. A 7.5 grams
sample contains 3 grams carbon, 0.5 grams hydrogen, and 4.0 grams
oxygen. Determine its molecular formula. (C = 12.0, H = 1.0, O = 16.0)
2. A chloride of sulphur was found to have a relative molecular mass of 135 g.
A 5.4 grams sample of the chloride was also found to contain 2.84 grams of
chlorine. Determine the molecular formula of the chloride. (C1 = 35.5, S =
32.0)
3. A hydrated salt of copper has the formula CuSO4. nH2O. About 25 grams of
the salt was heated until all the water evaporated. If the mass of the
anhydrous salt is 16.0 grams. Find the value of n. (Cu = 64.0, S = 32.0, O =
16.0, H = 1.0)
4. On complete combustion of one mole of a certain alkane, two moles of
carbon (IV) oxide and three moles of water were produced. Determine the
relative molecular mass of the alkane. (C = 12.0, H = 1.0)
5. If 7.36 grams of a compound decomposed to produce 6.93 grams of oxygen,
and the rest hydrogen. If the molecular mass of the compound is 34 grams.
Determine the molecular formula of the compound. (H = 1.0, O = 16.0)

Molar Solutions
A molar solution is a solution that contains one mole of a solute in one litre of
the solution. In this section, the terms concentration, molarity and dilution will
be discussed.
Concentration of a Solution
Concentration of a solution is the amount of a solute contained in a given
volume of the solution. Consider, 4.0 g of sodium hydroxide pellets dissolved in
200 cm3 of distilled water, and then made up to 250 cm3 of solution by adding
enough distilled water. The concentration of this solution could be expressed as
4.0 g per 250 cm3 of solution.

Thus, 250 cm3 of solution in which 4.0 g of sodium hydroxide is dissolved

contains 0.1 mole of sodium hydroxide. The concentration of the solution can,
therefore, be expressed as 0.1 mole per 250 cm3 of solution.
It can be seen that the concentration of a solution may be expressed in terms
of mass of solute in grams per given volume or number of moles of the solute
per given volume.
Worked Example 1
Suppose 4.0 g of sodium hydroxide were dissolved in 400 cm3 of distilled water
then made up to 500 cm3 of solution, determine the concentration in:
(a) grams.
(b) moles.
Solution
(a) The concentration is 4.0 g/500 cm3 of solution.
(b) The concentration is 0.1 mole/500 cm3 of solution.
For uniformity, concentration is normally expressed in either grams per litre of
solution (g/dm3) or in moles per litre of solution (mol/dm3).
Thus, using the data from the worked example 1:
Mass in 500 cm3 = 4.0 g

Moles in 500 cm3 = 0.1 mole

Note:
1 litre = 1000 cm3 = 1 dm3

Thus, the concentration of the solution would be expressed as 8.0 g/dm3 or

0.2 mole/dm3.
It can be shown that 1 cm3 of 4 g/500 cm3 solution and 1 cm3 of 8.0 g/1000
cm3 contain the same mass of the solute.
(i) Mass in 500 cm3 = 4.0 g
Mass in 1 cm3 = = 0.008 g cm-3
(ii) Mass in 1000 cm3 = 8.0 g
( Mass in 1 cm3 = cm3 = 0.008 gcm-3

Thus, the concentration of a 500 cm3 solution containing 4 g of solute is the

same as the concentration of a 1000 cm3 solution containing 8 g of solute.
Molarity of a Solution
Unlike concentration, molarity is given only in moles of the solute per litre of
solution (moles/100 cm3). This is normally expressed as mol dm-3.
Worked Example 2
Suppose 71g of sodium sulphate are dissolved in enough water then made to one
litre of solution. Determine the molarity of the solution formed. (Na = 23, S =
32, O = 16).

Mass of Na2SO4 dissolved = 71.0 g

Mass of 1 mole of Na2SO4 = 142 g
No. of moles in 1 dm3 = = 0.5 mole dm-3
Molarity is 0.5 M Na2SO4.

Exercise 2
1. Determine the molarity of a solution containing 10.6 g of sodium carbonate
dissolved in:
(a) 250 cm3 of distilled water.
(b) 500 cm3 of distilled water.
(Na = 23, C = 12, O = 16).
2. Calculate the number of moles of sodium carbonate present in 100 cm3 of 2
M Na2CO3 solution.
3. Calculate the mass of sulphuric(VI) acid in 250 cm3 of a solution whose
concentration is 0.25 mole dm-3.
4. Calculate the:
(a) Number of moles present in 25 cm3 of a 0.2 M Sodium hydroxide
solution.
(b) Mass in grams present in 25 cm3 of a 0.2 M Sodium hydroxide
solution. (Na = 23, O = 16, H = 1).
5. Calculate the number of moles of sodium chloride in 500 cm3 of 3 M
sodium chloride solution.
6. Calculate the mass of calcium chloride (CaCl2,) required to make one litre of
0.2 M calcium chloride solution.
7. When 34.8 grams of potassium sulphate (K2SO4,) were dissolved in 500cm3
distilled water. Calculate:
(i) The concentration of potassium sulphate in g/litre.
(ii) The molarity of the solution. (K = 39.0, S = 32.0, O = 16.0)
Preparation of Molar Solutions
The apparatus used to prepare molar solutions include volumetric flasks, and
measuring cylinders.

Fig 2.3: Volumetric analysis apparatus

Volumetric flasks come in different sizes. For example, 250 cm3. 500 cm3 and
1000 cm3. Preparing a solution involves dissolving the required mass of the
solute in a little water say, 100 cm3 of distilled water in a beaker. When all the
solute has dissolved, the solution is transferred to the volumetric flask. The
beaker is rinsed and the solution is transferred into the flask.
The solution is then made up to the mark on the narrow neck of the flask. The
flask is then stoppered. The neck of the flask is narrow to ensure high accuracy
of the instrument. The flask is then shaken to obtain a uniform solution.

A student using a wash bottle.

Experiment 2.5: How is a molar solution of sodium hydroxide
prepared?
Weigh accurately 40.0 g of sodium hydroxide pellets, put them in 200 cm3 of
distilled water in a 250 cm3 beaker and stir to dissolve. When all the solid has
dissolved, transfer the solution into a one-litre volumetric flask. Rinse the beaker
with some distilled water, and transfer the solution into the volumetric flask.
Using distilled water in a wash bottle, make up the solution to the mark. Repeat
the procedure using exactly 20.0 g and 10.0 g, of sodium hydroxide, prepare the
solutions in 500 cm3 and 250 cm3 volumetric flasks respectively.

Answer the following questions

1. Calculate the number of moles of sodium hydroxide in the:
(a) 1 litre solution.
(b) 500 cm3 solution.
(c) 250 cm3 solution.
(Na = 23, O = 16, H = 1).
2. Determine the molarity of the solutions of sodium hydroxide in (1) (a), (b)
and (c). Comment on the results.

Discussion
The number of moles in each of the solutions prepared is calculated as follows:
 Note:
The molarity of the solutions prepared
in (a), (b) and (c) is the same. The
results of this experiment show that to
prepare a molar solution, one does not
have to disolve a mass of one mole of a
solute in enough water, and make up to
one litre of solution.

Then the actual molarity of each of the solutions is calculated as follows.

2. (a) No. of moles in 1000 cm3 = 1.0 mole dm-3
Molarity is 1.0 M NaOH.
(b) No. of moles in 500 cm3 = 0.5 mole
No. of moles in 1000 cm3

Molarity is 1.0 M NaOH.

(c) No. of moles in 250 cm3 = 0.25 mole
 No. of moles in 1000 cm3 = = 1.0 mole dm-3
Molarity is 1.0 M NaOH.

Exercise 2.8
1. Explain how a 250 cm3 solution of 1.0 M potassium hydroxide solution can
be prepared. (K = 39, O = 16, H = 1).
2. Calculate the mass of lead nitrate, Pb(NO3)2 required to make 500 cm3 of a
0.1 M solution. (Pb = 207.0, N = 14.0, O = 16.0)
3. Find the mass of nitric acid required to prepare 25 cm3 of a 12.6 g per litre
of nitric acid solution. (O = 16, N = 14, H = 1)
4. In a class of 25 students, each student requires 120 cm3 of 0.2 M potassium
hydroxide solution for a titration experiment. Calculate:
(i) The total volume of potassium hydroxide required for the class. (K =
39, O = 16, H = 1)
(ii) The total mass of potassium hydroxide required to prepare the total
volume of solution for the class.
5. Calculate the molarity of a solution of sulphuric (IV) acid (H2SO4) that is
obtained by dissolving 9.8 g of sulphuric(IV) acid in 100 cm3 of solution. (S
= 32, O = 16, H = 1)
Dilution of a Solution
Dilution is a process by which the concentration of a solution is lowered by
adding more solvent into the solution. During dilution, the amount of solute
remains the same as the volume of the solution increases.

Experiment 2.6: How are solutions diluted?

Measure accurately 25 cm3 of 2 M HCl. Transfer the solution into a 250 cm3
volumetric flask. Add distilled water to the acid and make up to 250 cm3 of
solution. Repeat the process using a 500 cm3 volumetric flask instead of the 250
cm3 flask.

Answer the following questions

 1. Determine the number of moles in the 25 cm3 of the 2.0 M HCl.
2. Determine the molarity of the solution contained in the:
(i) 250 cm3 flask.
(ii) 500 cm3 flask.
(iii) Comment on the results.
3. Derive a general formula of preparing a less concentrated solution from a
more concentrated solution.

Discussion
The concentrations of the diluted solutions are obtained as follows:

Although equal volumes of solution containing equal moles were diluted, the
molarities of the resulting solutions are different. The solution to which less
water was added is more concentrated than the one to which more water was
added.
Solutions of different molarities may be prepared by adding water to equal
volumes of solutions of the same concentration and making up to different
volumes.
From the answers to Question 1 and 2, it can be seen that the molarity of the
dilute solution (M2) is obtained by multiplying the molarity of the concentrated
solution (M1) with the volume of the concentrated solution (VI), and dividing by
the final volume of the dilute solution (V2);
Thus: M2 =
Therefore, M2V2 = M1V1
The following worked examples show how this relationship is applied in
calculations.

Example 1
Calculate the volume of a 5.0 M H2SO4 solution that will be required to make a
1000 cm3 solution of 0.05 M H2SO4.

Solution
M1V1 = M2V2
M1 = 5.0 M, V1 = ? M2 = 0.05 M, V2 = 1000 cm3

Example 2
When 50 cm3 of 2M potassium hydroxide solution was diluted, the final
concentration was O.1M. Calculate the volume of the diluted solution.
Solution:

Example 3
Calculate the volume of 18 M sulphuric(IV) acid, H2SO4, that will be required to
prepare 3.6 litres of 0.2 M sulphuric(VI) acid.
Solution
From M1V1 = M2V2

Example 4
A label on a bottle containing sulphuric(IV) acid has the following information:
• Density = 1.836 g/cm3
• Percentage purity = 98%
• Relative formula Mass = 98
Calculate:
(a) The concentration of the acid.
(b) The volume of the concentrated sulphuric(VI) acid that should be diluted to
produce 2 litres of 2 M sulphuric(VI) acid.
Solution:
Exercise 2.9
1. About 250 cm3 of a 2 M sodium hydroxide solution is diluted to 2000 cm3.
Calculate the new concentration.
2. Calculate the volume of 18.4 M sulphuric(VI) acid, H2SO4, that will be
required to prepare 500 cm3 of a 2 M sulphuric(VI) acid solution.
3. Calculate the volume of 5.0 M HCl solution that would be required to
prepare 400 cm3 of 0.8 M HCl solution.
4. Calculate the volume of water that is to be added to 20 cm3 of 12.4 M
hydrochloric acid, HCl solution to make 2 M solution.
5. A bottle containing nitric(V) acid has a label with the following information;
• Density = 1.44 g cm–3
• Relative formula Mass = 63
• Percentage purity = 65%
(a) Calculate the concentration of nitric(V) acid, HNO3, in moles per litre.
(b) What will be the concentration of a solution prepared by diluting 20
 cm3 of the concentrated acid to make 250 cm3 of the acid solution.

Stoichiometry of Chemical Equations

Information about a chemical reaction can be represented by a word equation or
a chemical equation. A chemical equation is represented by means of chemical
symbols and formula for both the reactants and products. When particles
combine in a chemical reaction, they do so in specific proportions.
For example, A + B AB
The reacting amounts of A and B can be expressed in terms of moles. The
proportion in which they combine is referred to as mole ratio. Knowledge of
reacting mole ratios of substances in a chemical reaction can be used to write a
balanced chemical equation for the reaction.
For one to write a balanced chemical equation, the following steps should be
followed:
(i) Reactants and products must be known.
(ii) Write a word equation.
(iii) Write in symbols the correct formulae for the reactants and products.
(iv) Balance the number of atoms of each kind on both sides of the equation.
(v) Include the state symbols for the reactants and the products.
In a balanced chemical equation, the quantities of reactants and products are
in a whole number ratio. For example in the equation;
2Mg(s) + O2(g) 2MgO(s),
The reactants and product are in the ratio 2:1:2.
A chemical equation in which the reactants and products are in whole
number ratios is called a stoichiometric equation. Stoichiometry is a
quantitative relationship between reactants and products in a chemical reaction.
When a chemical reaction takes place between aqueous ionic compounds,
only certain ions combine to form either a solid, liquid or gas. Consider the
reaction between magnesium sulphate and lead(II) nitrate solutions. Aqueous
magnesium sulphate contains magnesium and sulphate ions while lead(II) nitrate
contains lead(II) ions and nitrate ions.
 When the two solutions are mixed, lead ions, and sulphate ions react to form
the insoluble lead sulphate.

Ionic equation
Pb2+(aq) + SO42-(aq) PbSO4(s)
Magnesium ions and nitrate ions do not undergo change during the above
reaction. Ions which do not undergo change in a chemical reaction are called
spectator ions and are usually omitted when writing the ionic equation. There
are three possibilities during ionic changes:
(i) Formation of a precipitate (solid).
(ii) Evolution of a gas.
(iii) Formation of a liquid.
The ionic equations below illustrate the three possibilities.
CaCl2(aq) + Na2CO3(aq) CaCO3(s) + 2NaCl(aq)
Ionic Equation:
CaCO3(s) + 2HNO3(aq) Cu(NO3)2(aq) + CO2(g) + H2O(l)
Ionic Equation: CuCO3(aq) + 2H+(aq) Cu2+(aq) + CO2(g) + H2O(l)
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
Ionic Equation: H+(aq) + OH-(aq) H2O(l)

Experiment 2.7: What is the equation for the reaction between iron
metal and copper(II) sulphate solution?
Weigh accurately 0.56 g of freshly acquired iron filings and put them in a clean
dry weighed beaker. Take about 20 cm3 of 2 M copper(II) sulphate solution and
transfer it into a clean boiling tube, and heat it until it is nearly boiling. Add the
hot copper (II) sulphate solution to the iron filings in the beaker and stir the
mixture to cool and record your observations.
Carefully decant as much of the liquid as possible, ensuring that no solid is
lost. Wash the solid twice with distilled water. Place the beaker with the solid
residue on a sand bath. When the solid is sufficiently dry remove the beaker
from the sand bath and allow to cool. Weigh the beaker again with its contents.
Record your results as in table 2.11. See figure 2.4.
Fig. 2.4: Preparation of Iron(II) sulphate.

Table 2.11. Displacement of copper(II) ions by iron

Mass of beaker

Mass of beaker + iron filings

Mass of beaker + solid residue

Mass of iron filings

Mass of solid residue

Answer the following questions

1. What observations were made when iron filings and copper(II) sulphate
reacted?
2. Why was it necessary to use excess copper(II) sulphate?
3. Calculate the:
(i) Number of moles of iron metal reacted.
(ii) Number of moles of copper metal displaced from the solution. (Fe =
56, Cu = 63.5).
4. Write the equation of the reaction between iron and copper ions in
solution.
 5. What are the sources of error in this experiment?

Discussion
When iron reacts with copper ions in solution, the products formed are brown
copper metal and iron(II) sulphate in solution.
Copper(II) sulphate + Iron metal Iron(II) sulphate + Copper metal.
To ensure that all the iron metal used is reacted, blue copper(II) sulphate is
used in excess, hence the solution remains blue when the reaction is completed.
Table 2.12: Sample results

Mass of iron filings 0.56 g

Mass of copper displaced 0.64 g

From the masses of iron metal used, and the copper metal displaced from the
solution, the reacting mole ratio of iron metal and copper ions in solution can be
calculated.

Moles of iron used = = 0.01 mole

Moles of copper metal displaced = = 0.01007 mole

Thus, Fe: Cu2+

0.01: 0.01007
1.0: 1.007
Whole number mole ratio 1:1
Hence, one mole of iron atoms reacts with one mole of copper ions to
produce one mole of atoms of copper metal. Since one mole of copper sulphate
contains one mole of copper atoms, the equation of the reaction is
Fe(s) + CuSO4(aq) Cu(s) + FeSO4(aq)

Experiment 2.8: What is the equation for the reaction between

lead(II) nitrate and potassium iodide?
Take six test-tubes and label them, 1 to 6. Run 5 cm3, of 1.0 M potassium iodide
solution from a burette into each one of them. Add 1.0 cm3 of 1.0 M lead(II)
nitrate solution to the test-tube labelled 1, and stir the mixture well with a glass
rod. Add about 5 drops of ethanol to the mixture, stir, and place it in a test-tube
rack.
Add 1.5 cm3, 2.0 cm3, 2.5 cm3, 3.0 cm3 and 3.5 cm3 of the 1.0 M lead(II) nitrate
to the test-tubes labelled 2, 3, 4, 5, and 6 respectively. Add about 5 drops of
ethanol to each test-tube, stir and allow to settle. Measure the height of the
precipitate in each tube in (mm) and record the measurements in table 2.13. Plot
a graph of the heights of the precipitate against the volume of lead(II) nitrate
solution added.
Table 2.13: Height of the precipitate and volume of Pb(NO3)2 (aq) used

Answer the following questions

1. What was observed on mixing the two solutions?
2. What was the purpose of adding ethanol to the mixture?
3. Calculate:
(a) Number of moles of KI in 5 cm3 of 1.0 M KI solution.
(b) Number of moles of Pb(NO3)2 which reacted completely with 5.0 cm3
of 1.0 M KI.
4. The heights of the precipitate remained constant in the test-tubes labelled
4, 5 and 6. Explain.
5. How many moles of KI would react with one mole of lead(II) nitrate?
6. Write:
(a) Balanced chemical equation.
(b) Ionic equation for the reaction between lead(II) nitrate and potassium
iodide.
7. Comment on the shape of the graph of height of precipitate against volume
of the lead(II) nitrate.
Discussion
When lead(II) nitrate solution reacted with potassium iodide solution, a bright-
yellow precipitate of lead(II) iodide was formed. The insoluble lead(II) iodide
settled at the bottom of the test-tube when allowed to rest.
Sample results

Ethanol was added to the mixture to speed up the settling of the precipitate.
Warming the mixture also hastens the settling process. The heights of the
precipitate in test-tubes labeled 4 to 6, remained constant because lead(II) ions
were in excess and all the iodide ions had reacted. When a graph of height of
precipitate is plotted against volume of 1M Pb(NO3)2, the graph takes the
following shape.

The moles of iodide ions and lead ions that react are calculated as follows:
(i) Moles of KI in 5.0 cm3 = = 0.005 moles.
(ii) Moles of Pb(NO3)2 that reacted completely, = 0.0025
moles.

The stoichiometric equation for the reaction is:

Pb(NO3)2(aq) + 2KI(aq) PbI(s) + 2KNO3(aq)
It should be noted that both the lead(II) ions (Pb2+) and iodide ions (1–) have
undergone a chemical change. However nitrate ions and the potassium ions
remained unchanged after the reaction. The equation for the reaction can
therefore be represented as:
Pb2+ (aq) + 2I–(aq) PbI2(s)

Experiment 2.9: What is the equation for the reaction between

barium ions and carbonate ions?
Measure exactly 25.0 cm3 of 0.2 M barium chloride solution, and place it in a
beaker. Add 25 cm3 of 0.2 M sodium carbonate solution. Stir the mixture and
allow it to settle. Filter the solution, and dry the solid residue between a filter
paper. Do not dry by heating. Transfer the dry solid onto a filter paper which you
have weighed and recorded its weight. Record your results.

Answer the following questions

1. What ions are present in:
(a) barium nitrate solution?
(b) sodium carbonate solution?
2. What observations were made when the two solutions were mixed?
Explain.
3. The solid residue is not dried by heating. Explain.
4. Calculate the number of moles of barium ions and carbonate ions used in
the reaction. What assumptions have you made?
5. Calculate the number of moles of barium carbonate formed.
 6. What is the whole number ratio of barium carbonate formed to that of
barium ions and carbonate ions used?
7. Write the:
(i) stoichiometric equation.
(ii) ionic equation for the reaction.

Discussion
When salts dissolve in water, they ionise into their constituent ions. Sodium
carbonate and barium chloride when dissolved in water break into Na+ and
ions, Ba2+ and CI– ions respectively. On mixing the solutions, barium ions
combine with carbonate ions to form insoluble barium carbonate. Sodium and
chloride ions remain in solution unchanged. The following is the word equation
for the reaction:

Assuming that 25.0 cm3 of 0.2M sodium carbonate reacted completely with 25.0
cm3 of 0.2 M barium chloride.
(a) Moles of barium chloride used

Suppose sample results show that 0.985 g of barium carbonate were formed,
then:

It should be noted that one mole of barium chloride reacts with one mole of
sodium carbonate to produce one mole of barium carbonate. Thus the equation
for the reaction is:
BaCl2(aq) + Na2CO3(aq) BaCO3(s) + 2NaCl(aq)
The ionic equation for the reaction is:
.
The barium carbonate obtained should not be dried by heating because the
compound easily decomposes on heating.

Experiment 2.10: What is the equation of reaction between

hydrochloric acid and sodium carbonate?
Weigh a polythene bag and a rubber band and record their masses. Place 2.65
g of sodium carbonate in a conical flask. Stopper the flask with a cork fitted with
a thistle funnel and delivery tube. Connect the delivery tube to the weighed
polythene bag and tie the mouth of the bag tightly with the rubber band as shown
in figure 2.5.

Fig. 2.5: Collecting a sample of Carbon(IV) oxide.

Measure exactly 50.0 cm3 of 1M hydrochloric acid solution and transfer the
acid to the thistle funnel. Run the acid from the thistle funnel into the conical
flask. Collect the gas evolved in the bag. Remove the bag when the reaction has
stopped. Weigh the bag with the gas again and record the mass.

Answer the following questions

1. Calculate:
(a) Moles of the acid used.
(b) Moles of the gas collected.
2. Write the equation for the reaction between hydrochloric acid and sodium
carbonate.
 3. What are the likely sources of error in this experiment?

Discussion
In this reaction, hydrogen ions from hydrochloric acid react with carbonate ions
from sodium carbonate to form water and carbon(IV) oxide.

Assuming all the acid and carbonate reacted and the mass of carbon(IV) oxide
collected was found to be 1.1g, then, moles of carbon(IV) oxide
= 0.025 mole.
Thus, 0.025 moles of (aq) reacted with 0.05 moles of H+(aq) to form
0.025 moles of carbon(IV) oxide.

The ionic equation is:

and the stoichiometric equation is

2HCl(aq) + Na2CO3(aq) 2NaCl(aq) + CO2(g)+ H2O(l)

Exercise 2.10
1. A sample of 2.34 g of a metal T displace 3.20 g of copper from excess
aqueous copper(II) sulphate. (T = 69, Cu = 64).
(a) Determine the charge on an ion of metal T.
(b) Write an ionic equation for the reaction.
2. A sample of 2.4 grams of magnesium were burnt in 1.6 grams of oxygen
gas. The magnesium oxide formed had a mass of 4.0 grams. Determine the
equation for the reaction from the given information. (Mg = 24, O = 16)
3. If 25 cm3 of a 0.1 M Na2CO3 solution neutralised a solution containing 2.5 g
sulphuric(VI) acid, H2SO4, in 250 cm3 of solution:
(a) Calculate the molarity of sulphuric(IV) acid, and the volume of the acid
 used.
(b) Write the equation for the reaction from this information.

Volumetric Analysis
Volumetric analysis is a method of quantitative chemical analysis in which the
amount of a substance is determined by measuring volumes of solution. Two
solutions are usually considered. One solution of known concentration and
volume is reacted carefully with another of unknown concentration to determine
the reacting volumes. This data is used to determine the concentration of the said
solution. The above procedure is also called titration.
A solution whose exact concentration is known is called a standard
solution. The apparatus used in volumetric analysis are pipettes and burettes.
A pipette is designed to deliver a definite volume of a solution, e.g., 10.0
cm3, 20.0 cm3 or 25.0 cm3.

A pipette filler precludes the chance of sucking liquids into the mouth.

Before use, the pipette must be rinsed with the solution to be drawn. It is then
filled by sucking the liquid to a few centimeters above the calibration mark.
The solution is then allowed to drain slowly under gravity until the meniscus
is at the same level with the mark. Sucking can be done using the mouth or a
pipette filler. Pipette fillers must be used especially when solutions are toxic.
Automatic pipettes that dispense the exact amount of liquid required are also
available. A burette is designed to deliver variable volumes of solution as needed
during a titration. It is graduated from 0.0 to 50.0 cm3 with unit intervals of
0.1cm3.
Before use, a burette must be rinsed with the solution to be used in it. It is
then filled carefully beyond the 0.0 mark and the level of the solution is adjusted
until the bottom of the meniscus is at the same level with the graduation mark.
Titration
Titration is a quantitative analysis process using solutions. A solution of known
concentration is added gradually to another solution of unknown concentration
until the reaction between the two solutions is complete. The point at which the
reaction is complete is called the end point. An indicator is used to identify the
end point.
The volume of the solution that run out of the burette in every titration
experiment is known as a titre. After the titration the data should be arranged in
tabular form as shown in table 2.14. The volume of the pipette used should be
shown always.
The volume of pipette used ..................................... cm3.

A titration in progress.

Table 2.14: Table of results of a titration experiment

Average volume used = ..................................... cm3.
Average titre = ..................................... cm3.
The titre should be recorded in one or two decimal places. When in two decimal
places, the last digit should be zero or five. The volumes used for the three
experiments should be consistent and have an accuracy of ± 0.2 cm3. The
average titre is given by adding the volumes of the consistent titres used divided
by number of experiments done.
Indicators are useful in pointing out the precise end-point of a titration. The
choice of an indicator for every titration experiment therefore depends on its
properties as shown in table 2.15.
Table 2.15: Properties of indicators used in titrations

Choice of Indicators
The table bellow is a guide on how to choose an appropriate indicator for
different acid base titrations.

Titration Suitable Indicator for use

Strong acid Strong alkali Any indicator

Strong acid Weak base Screened methyl orange or methyl orange
Weak acid Strong base Phenolphthalein
In this book, three types of titrations will be discussed; direct titration, back
titration and redox titration.
Direct Titration
This is a type of titration that involves the addition of a standard solution to a
fixed volume of the analyte (substance being anlaysed), or vice versa with the
sole aim of determining either:
(a) Concentration.
(b) Relative atomic mass of the elements of the sample analyte or,
(c) The percentage composition of the constituent elements. A good example is
a netralisation reaction.

Experiment 2.11 (a): What is the equation for the reaction between
sodium hydroxide and hydrochloric acid?
Using a pipette, transfer 25 cm3 of 0.1 M sodium hydroxide solution into a
conical flask. Add 2 drops of phenolphthalein indicator. Fill a clean burette with
0.1 M hydrochloric acid and read the initial level of the acid accurately.
Remember to read the lower level of the meniscus.
Run the acid solution in about 1 cm3 portions, swirl the liquid in the flask
after each addition of the acid. After several such additions, the pink colour in
conical flask will start disappearing on shaking. When this happens, the reaction
is near the end-point. Add the acid drop-wise, until that point when only one
drop of the acid changes the colour of the solution to colourless permanently.
Record the final reading of the burette accurately remembering to read the
lower level of the meniscus. Rinse the conical flask and repeat the experiment.
Record the results as shown in table 2.18.
Table 2:18: Titration of sodium hydroxide with dilute hydrochloric acid

The volume of the pipette used is .............................. cm3.

Average volume of acid used cm3.

Answer the following questions

1. What was the volume of hydrochloric acid that reacted with 25 cm3 of 0.1
M sodium hydroxide solution?
2. How many moles of hydrochloric acid are there in the average titre?
3. How many moles of sodium hydroxide are there in 25 cm3 of 0.1 M
sodium hydroxide solution?
4. Write down the equation for the reaction between hydrochloric acid and
sodium hydroxide.

Discussion
The reaction between hydrochloric acid and sodium hydroxide is complete at the
end point when the indicator changes from pink to colourless. Taking the
average titre as 25.0 cm3, therefore the number of moles of hydrochloric acid
used are:

Number of moles of sodium hydroxide used are:

It means that the mole ratio of acid to base is: 1:1, therefore, the equation is
written as:
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(1).
Mole ratio: 1:1.
The reaction between an acid and an alkali forms a salt and water only. This
kind of reaction is called neutralisation.
The ionic equation is
H+(aq) + OH–(aq) H2O(l)

Experiment 2.11(b): What is the equation for the reaction between

sodium hydroxide and sulphuric(VI) acid?
Pipette 25.0 cm3 of 0.1 M sodium hydroxide solution in to a conical flask. Add 2
drops of phenolphthalein indicator and titrate with 0.1 M sulphuric(VI) acid
from a burette. Record the results as shown in table 2.19.
Table 2.19: Titration of sodium hydroxide with sulphuric(VI) acid
Volume of pipette used ..................................... cm3

Average volume acid used (cm3)

Answer the following questions

1. What volume of sulphuric(VI) acid neutralised 25 cm3 of 0.1 M sodium
hydroxide solution?
2. How many moles of sulphuric(VI) acid are there in the average titre?
3. How many moles of sodium hydroxide are there in 25 cm3 of 0.1 M
sodium hydroxide?
4. How many moles of sodium hydroxide react with 1 mole of sulphuric(VI)
acid? Write the equation for the reaction.
5. From experiment 2.11(a), and 2.11(b) compare the volumes of 0.1 M
sulphuric(VI) acid and 0.1 M hydrochloric acid which neutralise 0.1 M
sodium hydroxide solution in each case.

Discussion
Taking the average titre as 12.5 cm3 of sulphuric(VI) acid, then:
Moles of sulphuric(VI) acid = × 0.1 = 0.00125.
Moles of sodium hydroxide = × 0.1 = 0.0025.
The mole ratio of sulphuric(VI) acid: sodium hydroxide is 0.00125: 0.0025
which is 1: 2. Therefore, equation for reaction is:
 H2SO4(aq) + NaOH(aq) Na2SO4(aq) + 2H2O(aq)
Ionic equation:
2H+(aq) + 2OH–(aq) 2H2O(1)
Comparing experiment 2.11 (a) and 2.11 (b) the volume of 0.1 M hydrochloric
acid is twice the volume of 0.1 M sulphuric acid that reacted with 0.1 M sodium
hydroxide solution. This means that sulphuric acid is able to release twice the
number of hydrogen ions as compared to hydrochloric acid.
The number of hydrogen ions which can be produced by a molecule of an
acid on ionising is referred to as the basicity of the acid. Thus, the basicity of
HCl and HNO3 is one (1) while that of H2SO4 and (HOOC–COOH) ethanedioic
acid is two(2). See table 2.20.
Table 2.20: Basicity of common acids

For example:

In ethanoic acid only one hydrogen atom is replaceable, the one attached to O–
H, the others are not replaceable.

Experiment 2.12: How can hydrochloric acid solution be

standardised using sodium carbonate?
Put about 100 cm3 of distilled water in 250 cm3 volumetric flask. Measure 2 cm3
of concentrated hydrochloric acid in a 10 ml measuring cylinder and transfer it
to the flask. Add distilled water to make up to the 250 cm3 mark. Rinse the
burette with the acid. Pour the acid solution into the burette.
Weigh exactly 1.325 g of anhydrous sodium carbonate, dissolve in water and
make up to 250 cm3 in a flask. Transfer 25 cm3 of the sodium carbonate solution
using a pipette into a conical flask. Add 2 or 3 drops of methyl orange indicator
and titrate with the hydrochloric acid solution until the indicator changes colour
from yellow to pink. Record your data in table 2.21.
Table 2.21: Standardisation of hydrochloric acid
Volume of pipette used is 25 cm3

Answer the following questions

1. What is the meaning of the term 'standardisation'?
2. Determine the average volume of acid used.
3. Write the equation for the reaction between sodium carbonate and
hydrochloric acid.
4. Determine:
(a) The molarity of the sodium carbonate solution.
(b) The number of moles of sodium carbonate that reacted with the acid.
5. Determine the number of moles of acid used.
6. Calculate the concentration of the acid in:
(a) mol dm.–3
(b) g dm.–3

Discussion
Standardisation is the process by which an unknown concentration of a solution
is determined by use of a standard solution in a titration experiment. Suppose the
average volume of the acid used is 22.5 cm3, the concentration of the acid can be
determined as follows:
Na2CO3(aq) + 2HCI (aq) 2NaCI(aq) + CO2(g) + H2O(l)
Mole ratio: 1: 2. Relative formula mass of Na2CO3 is 106 g.
If 1.325 g of Na2CO3 was dissolved in 250 cm3, then in 1000 cm3, the mass
would be:

Hence, molarity

Moles of Na2CO3 in 25 cm3

Mole ratio Na2CO3: HCl is 1: 2.

Therefore, moles of HCl in 22.5 cm3 = 2 × 0.00125 = 0.0025 mole.

Hence, moles of HCl in 1000 cm3
Molarity of hydrochloric acid is 0.11 M. Giving concentration in grams/litre.
Molar mass of HCl is 36.5 g. Concentration of HCl in grams/litre is:
36.5 × 0.11 = 4.015 grams/litre = 4.0 g/L.

Back Titration
Back titration is a method of volumetric analysis used to determine the
concentration (or amount) of a reactant. It involves reacting quantities of the
substance being analysed with an excess amount of a suitable reagent whose
volume and concentration is known. The quantity of the excess is then measured
through titration. The amount of the reagent that reacted with the analyte is
determined by subtracting the excess amount from the initial. The data is then
used to determine the concentration (or amount) of the analyte.

Experiment 2.13: What is the atomic mass of divalent metal M?

Weigh exactly 0.50 g of a divalent metal carbonate, MCO3. Put the weighed
carbonate in a conical flask. Add to it 30.00 cm3 of 0.50 M hydrochloric acid.
Add two to three drops of phenolphthalein in the resulting solution. Titrate the
solution against a 1.0 M sodium hydroxide solution until the colour of the
solution just turns pink permanently. Record your results in table 2.22. Repeat
the experiment three times to complete the table.
Table 2.22: Neutralisation reaction

Answer the following questions

1. Calculate the average volume of base used to neutralise the excess acid.
2. Determine:
(a) The number of moles of base used.
(b) (i) The volume of acid that was neutralised by the base.
(ii) The number of moles of acid that reacted with the carbonate.
3. (i) Write the equation for the reaction between the acid and carbonate.
(ii) Determine the number of moles of the carbonate in the sample.
(iii) Determine the relative formula mass of the carbonate.
(iv) Determine the relative atomic mass of M.

Discussion
The following are sample results from a similar experiment:

The average titre (base) used is determined by considering the values which are
consistent to within ± 0.20 range only.

From the sample the results: Volume of base that neutralised excess acid =
5.0 cm3. Therefore, 1000 cm3 of base contains 1.0 mole.

The equation for the neutralisation reaction is:

HCl (aq) + NaOH (aq) NaCl (aq) + H2O (1)
Thus, the reacting mole ratio of acid to base, HCl: NaOH is 1: 1. Hence,
moles of excess acid neutralised was 0.005 mole. But, the molarity of the acid
was 0.50 M HCl and 0.50 moles was contained in a 1000 cm3.

Thus, volume of excess hydrochloric acid after reaction with the carbonate is
10.0 cm3. This means only 20.0 cm3 of the 30.0 cm3 of acid added to the
carbonate to completion.
1000 cm3 of acid contained = 0.50 mole.

But the equation of the reaction between the base and the acid is:

The reacting mole ratio of the carbonate to the acid is : 2

1
MCO3 : 2HCl
1 : 2

Thus moles of the carbonate that reacted with 0.10 mole of the acid is of 0.10
mole.
Mass of 0.005 mole = 0.50 g

Alternative Working

Redox Titrations
In redox reactions, both reduction and oxidation take place simultaneously.
Titrations involving redox reactions do not require indicators because the colour
of some of the reagents change when their oxidation states change. Examples of
redox titrations involve the use of potassium manganate(VII) and potassium
dichromate(VI). Manganate(VII) ions are purple in colour. When reduced to
manganese(II), the solution becomes colourless.

Dichromate(VI) ions are orange in colour. When reduced to chromium(III)

ions, the solution becomes green.

Redox titrations are used to standardise solutions and to determine the purity of
compounds. Potassium manganate(VII) and potassium dichromate(VI) solutions
should be acidified before use in titrations. This is done to ensure complete
reduction to manganese(II) and chromate(III) ions, respectively.

Experiment 2.14. How can potassium manganate(VII) solution be

standardised using iron(II) salt?
Weigh accurately 9.8 g of the iron(II) salt, FeSO4.(NH4)2SO4.6H2O) and
dissolve in distilled water that has been boiled and cooled to remove air. Add
more distilled water to make up to 250 cm3.
Transfer 25.0 cm3 of the solution into a conical flask using a pipette. Add 10 cm3
of dilute sulphuric acid and titrate with potassium manganate(VII) from a burette
until a persistent pink colour appears. Record the volume of potassium
manganate(VII) used. Repeat the experiment twice and record your results in
table 2.23.
Table 2.23 Standardisation of potassium manganate(VII)
Volume of pipette used is 25 cm3

Answer the following questions

1. Determine the average volume of potassium manganate solution.
2. Calculate the molarity of the iron(II) salt solution.
3. Calculate the number of moles of iron(II) ions used.
4. Given the equation of the reaction is:

Determine:
(a) The number of moles of ions in 24.0 cm3 solution.
(b) The molarity of the KMnO4(aq) solution.
Discussion
Suppose the average titre is 24.0 cm3. Molarity of the iron(II) salt = 392 g.
Number of moles of iron(II) ions in 250 cm3 solution =
Moles in 1000 cm3 = = 0.1 mole
Thus molarity of the iron(II) salt is 0.1 M. Number of moles of iron(II) ions in
25 cm3.
Solution, = = 0.0025 mole.
From the equations,

Therefore, moles of in 24.0 cm3, = 0.0025 ×

Experiment 2.15: What is the amount of water of crystallisation in

ammonium iron (II) sulphate?
Ammonium iron(II) sulphate crystals have the following formula (NH4)2SO4.
FeSO4. nH2O. Weigh accurately 8.8 g of the salt and dissolve in 50 cm3 of 2.0 M
sulphuric(IV) acid. Make up to 250 cm3 of solution with distilled water. Pipette
25.0 cm3 of this solution and pour it into a conical flask. Titrate this against the
acidified manganate(VII) used in experiment 2.14 until the solution becomes
colourless. Record your results in table 2.24.
Table 2.24: Titration of ammonium iron (II) sulphate using potassium manganate(VII)
 Answer the following questions
1. Calculate the:
(a) Average volume of KMnO4 solution used.
(b) Number of moles of KMnO4 that reacted.
2. Using the following ionic equation determine the number of moles of
iron(II) salt in 25 cm3 of the solution used.

3. Determine the molarity of the iron(II) salt solution.

4. Determine:
(a) The value of ‘n’ in the formula, (NH4)2SO4. FeSO4. nH2O.
(b) The formula of the iron(II) salt.

Discussion
Suppose the average volume of the 0.02 M KMnO4 solution used was 22.5 cm3,
then: Moles in 1000 cm3 = 0.02 mole.

However, 0.00225 mole were contained in 25 cm3.

That is, 25 cm3 contained = 0.00225 mole.

Hence, molarity of iron(II) salt is determined as follows:

250 cm3 contains 0.0225 mole

250 cm3 solution contains 8.8 g

Mass of 0.09 mole = 35.2 g

Therefore, formula of the salt is: (NH4)2SO4.FeSO4.6H2O

Exercise 2.11
1. 25.0 cm3 of 0.2 M solution of hydrochloric acid required 12.5 cm3 of
sodium hydroxide solution for complete neutralisation.
Calculate the concentration of sodium hydroxide in:
(i) moles per litre.
(ii) grams per litre.
2. About 100 cm3 of a solution of hydrochloric acid reacted completely with
0.12g of magnesium ribbon.
(a) Write the equation for the reaction.
(b) Calculate the concentration of the acid in moles per litre.
3. Solution R was made by dissolving 2.65 g of a metal carbonate, M2CO3 in
water and diluting to 250 cm3 of solution. Is a 0.25 M hydrochloric acid
solution. Then 25.0 cm3 portions of R were titrated with solution Q using
methyl orange indicator.
The following results were obtained.
 (a) What is the colour of the resultant solution at the end-point? 1.
(b) Calculate the average volume of Q used.
4. A solution of 25.0 cm3 of iron(II) ammonium sulphate needed exactly 20.0
cm3 of a solution of potassium dichromate(VI) of concentration 0.05 M.
(a) State the colour of the solution at the end-point.
(b) Given the equation:

Calculate the concentration of iron(II) ions in the iron(II) ammonium

sulphate.
5. When 4 g of a metal carbonate MCO3 was dissolved in 160 cm3 of 1 M
hydrochloric acid and then the resultant solution diluted to one litre, 25.0
cm3 of this solution required 20.0 cm3 of 0.1 M sodium hydroxide solution
for complete neutralisation, calculate:
(i) The number of moles per litre of excess hydrochloric acid that reacted
with sodium hydroxide, NaOH.
(ii) The number of moles per litre of acid that reacted with the carbonate.
(iii) The number of moles of carbonate, MCO3, that reacted with the acid.
(iv) The formula mass of the carbonate, MCO3.
(v) The atomic mass of the metal M.
(C = 12.0, 0 = 16.0)

Atomicity and Molar Gas Volume

Atomicity
Atomicity is the number of atoms in one molecule of an element. For example,
oxygen (O2), hydrogen (H2) and nitrogen (N2) have two atoms per molecule,
thus they are diatomic. Ozone (O3) has three atoms in a molecule and is
therefore triatomic. The noble gases are said to have an atomicity of one
(monoatomic) even though they are not molecular. Table 2.25 shows the
atomicity of some gases.
Table 2.25: Atomicity of some selected gaseous elements.

Gas Chemical formula Atomicity

Helium He 1

Argon Ar 1

Neon Ne 1

N2 2
Nitrogen
H2 2
Hydrogen
O2 2
Oxygen
Cl2 2
Chlorine
O3 3
Ozone
Bromine Br2 2

Molar Gas Volume

So far, reactions involving substances in solutions have been discussed. In this
section, reactions of substances in the gaseous state will be discussed.

Experiment 2.16: What is the volume occupied by one mole of a

gas?
Take three glass syringes each of 50 cm3. Lubricate the pistons of the syringes to
reduce friction. Push out all the air from the syringes. Plug the outlet of the
syringes, and weigh each syringe with its plug. Connect each syringe to a steady
supply of oxygen gas until the syringe is full of the gas to the 50 cm3 mark as
shown in figure 2.7. Plug the syringes and reweigh the syringes. Repeat the
experiment with carbon(IV) oxide and chlorine gas. Record your results in table
2.26. Workout the density, molar mass and volume occupied by one mole of
each gas to complete the table.

Figure 2.7: Measurement of gas volumes.

Table 2.26 Relationship between volume and mass in gases

Answer the following questions

1. Comment on the volume occupied by one mole of each of the three gases.
2. What is the average volume occupied by one mole of a gas expressed in
litres at room temperature and pressure (r.t.p.)?
3. What volume would one mole of the gas occupy at 0°C and 760 mmHg?
 4. What are the possible sources of error in this experiment?

From the table, it is observed that the volume occupied by one mole of each
gas is nearly the same. The volume of a gas depends on the prevailing conditions
of temperature and pressure.
The volume occupied by one mole of any gas at given temperature and
pressure is called the molar gas volume. Its value at s.t.p is 22.4 dm3. If the
volumes are worked out at another temperature and pressure, a different constant
value is obtained. For example, at 25°C, and one atmosphere pressure, the molar
gas volume is 24.0 dm3.
The conditions of temperature of 25°C and one atmospheric pressure are
called room temperature and pressure (r.t.p).
The results show that there is a relationship between the volume and mass of
a gas at given temperature and pressure. By knowing the mass of a given volume
of a gas at r.t.p. or s.t.p., the molar mass of the gas can be calculated.

Combining Volumes of Gases

This section deals with combining volumes of gases when they react at the same
temperature and pressure. For calculation involving gases, volumes are preferred
because the volumes are easier to measure than the masses.

Experiment 2.17: What are the combining volumes of ammonia gas

and hydrogen chloride at room temperature and pressure?
Push the pistons to the end of the syringes to remove all the air. Connect the first
syringe to dry ammonia gas generator and the second syringe to dry hydrogen
chloride gas generator, as shown in figure 2.6. Collect 30 cm3 of dry ammonia
gas in the first syringe. Collect 40 cm3 of dry hydrogen chloride gas in the other
syringe and clip as in figure 2.8 (a) and (b).
Figure 2.8(a) Empty Syringes

Fig 2.8(b): Samples of hydrogen chloride and ammonia gas.

Connect the two syringes with a glass tube as shown in figure 2.8(c) ensuring
the clips are tightly closed. Open the clips and push the gas from the first syringe
to the second and from the second to the first syringe. Read the volume of the
gas in each of the syringes. Repeat this process until a constant volume is
obtained. If there is any gas remaining in the syringe, record its volume and test
with moist litmus paper.

Fig. 2.8(c): Set-up for measuring reacting volumes of gases

Answer the following questions

 1. What observations are made when the two gases were mixed?
2. What is the residual gas? Explain.
4. Which gas is in excess?
5. Write the equation for the reaction.
6. What are the sources of error in this experiment?

Discussion
A white solid, ammonium chloride is formed in the glass tube when the two
gases react. Results of the experiment show that the volume of the residual gas is
10 cm3. When tested, the gas turns moist blue litmus red showing that it is
hydrogen chloride. This means that 30 cm3 of ammonia reacted with 30 cm3 of
hydrogen chloride.

These results show that the reacting volumes of gases are in a whole number
ratio.

Other experimental results show that volumes of reacting gases are always in a
simple whole number ratio and if the products of the reactants are gaseous, their
volumes are also in simple whole number ratio with the volumes of the reactants.
For example:

The relationship between reacting volumes of gases is summarised by Gay

Lussac’s Law: When gases react, they do so in volumes that bear a simple ratio
to one another and to the volumes of the product if gaseous, temperature and
pressure remaining constant.
Example 1
Example 2

It has also been found from experiments that equal volumes of all gases
under the same conditions of temperature and pressure contain an equal number
of molecules. This relationship leads to the Avogadros’ Law: “Equal volumes of
gases will contain equal number of molecules”. The number of molecules per
mole of any gas is 6.02 × 1023 and occupies a volume of 22.4 dm3 at s.t.p. The
number 6.02 × 1023 is known as the Avogadro’s number.
Avogadro’s law implies that volume ratios of reacting gases can be used
interchangeably with mole ratios when gases react. This means that reacting
volumes of gases can be used to determine the equation of reacting gases
provided the volumes are measured under the same conditions of temperature
and pressure.

Worked Examples
1. In an experiment, 20 cm3 of sulphur(II) oxide are found to react completely
with 10 cm3 of oxygen to produce 30 cm3 of sulphur(IV) oxide. Determine
the equation for the reaction.

So the balanced equation is:

2SO2(g) + O2(g) 2SO3(g)
2. When 100 cm3 of a gaseous hydrocarbon(CxHy) burn in 400 cm3 of oxygen,
100 cm3 of oxygen is unused, 200 cm3 of carbon(IV) oxide and 200 cm3 of
steam are formed. Deduce the equation for the reaction and the formula of
the hydrocarbon.
Solution

The formula deduced from reacting volumes is worked out as follows:

CxHy (g) + O2(g) 2CO2(g) + 2H2O(g)

Writing a balanced equation from the above:

C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(g)
The formula of the hydrocarbon is derived on the basis of the following facts:
(i) In a balanced chemical equation, the number of each kind of atoms on the
reactant side must be equal to that in the product side.
(ii) Hydrocarbons are compounds consisting of carbon and hydrogen only.

Exercise 2.12
1. If 0.32 g of oxygen, occupy 224 cm3 at s.t.p., calculate its relative formula
mass.
2. Calculate the volume occupied by one mole of hydrogen gas given that its
density is 0.09 g/litre. (H = 1.0)
3. Magnesium carbonate decomposes when reacted according to the equation.
MgCO3(s) MgO(s) + CO2(g)
Calculate the volume of carbon(IV) oxide which is produced when 8.4g of
the carbonate is decomposed at s.t.p. (Mg = 24.0, C = 12.0, O = 16.0)
4. Under the influence of a catalyst, ammonia reacts with oxygen according to
the equation:
4NH3(g) + 502(g) 4NO(g) + 5H2O(g)
 Given that 200 cm3 of ammonia were reacted with excess oxygen, calculate
the volume of nitrogen(II) oxide and steam produced.
5. About 40 cm3 of oxygen gas were reacted with 100 cm3 of hydrogen gas.
Determine the volume of the residual gases at 105°C.
6. Ammonia gas decomposes according to the equation:
2NH3 (g) N2(g) + 3H2(g)
Determine the volume of nitrogen and hydrogen produced if 30 litres of
ammonia gas is allowed to decompose completely.

Summary
1. The relative atomic mass of an element is the average mass of one of its
atoms on a scale where the carbon -12 isotope has a mass of 12.000 mass
units.
2. The number of atoms in one relative atomic mass in grams of any element is
6.023 × 1023. This number is referred to as the Avogadro’s Constant, 'L'.
3. The standard counting unit in chemistry is the Mole. It is the number of
particles in 12.0 g of the carbon -12 isotope.
4. The mass of one mole of a substance is called Molar Mass.
5. Empirical formula is the simplest ratio in which atoms combine to form a
compound.
6. To obtain the empirical formula, use the following steps:
(a) Find the mass in grams of the combining elements.
(b) Find the number of moles of each element by dividing the masses by
the respective R.A.M. ratio.
(c) Find the simplest whole number ratio.
7. Molecular formula shows the actual numbers of each kind of atom present
in one molecule of a compound.
8. The molecular mass of a compound is the sum total of the relative atomic
masses of the elements in one molecule of the compound. For ionic
compounds, it is referred to as formula mass.
9. The number of atoms in one molecule of an element is the atomicity.
10. One mole of any gas at standard temperature and pressure (s.t.p.) occupies
22.4 dm3 (litres).
11. At room temperature and pressure (r.t.p.), one mole of a gas occupies 24
dm3 (litres).
12. A volume of 22.4 dm3 of any gas has 6.023 × 1023 molecules.
13. Equal volumes of different gases at the same temperature and pressure
contain the same number of molecules.
14. Gay Lussac’s law states that: When gases react they do so in volumes which
bear a simple ratio to one another and to the volumes of the products if
gaseous, temperature and pressure remaining constant.
15. Avogadro’s law states that: Equal volumes of gases will contain equal
number of molecules.
16. In writing chemical equations, the following points are important:
(a) Know the reactants and products.
(b) Include state symbols in the equations.
(c) Balance the equation.
17. In writing an ionic equation, distinguish the substance that has free ions and
those without free ions. The equation consists of only those ions that
undergo change of state in the course of the reaction.
18. A molar solution is one, which contains one mole of the substance dissolved
in water and made up to one litre (or dm3) of solution.
19. A solution of known concentration is known as a standard solution.
20. Redox titrations do not require an indicator because the solutions themselves
will change colour with change of oxidation states of the reactants.
21. Note the following formulae are used in solving various problems involving
molar solutions.

Revision Exercise
1. Calculate the number of atoms in:
(a) 2.1 g of nitrogen.
(b) 13.8 g of sodium.
(c) 112 g of iron.
2. Calculate the mass in grams of:
(a) 0.02 moles of chlorine atoms.
(b) 0.6 moles of aluminium atoms.
(c) 8 moles of sulphur.
3. Calculate the number of moles of atoms in:
(a) 8 g of oxygen.
(b) 60 g of calcium.
(c) 1 g of neon.
4. Calculate the number of moles of molecules in:
(a) 48 g of sulphur(IV) oxide, SO2
(b) 9.8 g of sulphuric acid, H2SO4
(c) 21.3 g of chlorine gas, Cl2
5. Determine the formula mass of each of the following compounds:
(a) NH4C1
(b) NaHCO3
(c) FeCL3
(d) C2H5OH
(e) AL2(SO4)3
6. Calculate the mass of:
(a) 0.1 mol of H2SO4
(b) 1.5 mol of NaOH
(c) 0.05 mol of PbO2
(d) 1.60 mol of NH3
7. Calculate the number of moles of molecules in:
(a) 4.4 g of carbon(IV) oxide, CO2
(b) 7.30 g of hydrogen chloride, HCl
(c) 32 g of sulphur(IV) oxide, SO3
(d) 13.2 g of propane, C3H8
8. How many atoms are there in:
(a) 0.5 moles of ammonia, NH3(g)?
 (b) 2.0 mol of hydrogen chloride gas, HCl?
(c) 0.15 mol of carbon(II) oxide gas, CO?
9. Work out the formulae of compounds which have the following percentage
composition by mass:
(i) Sodium 43.40%, carbon 11.30% and oxygen 45.30%.
(ii) Magnesium 9.8 %, sulphur 13.0%, oxygen 26.0% and water of
crystallisation 51.2%
(H = 1, C = 12, O = 16, Na = 23, Mg = 24).
10. When 3.18 g of copper(II) oxide were carefully heated in a stream of dry
hydrogen, 2.54 g of copper and 0.72 g of water were formed. Determine the
number of moles of hydrogen atoms which combine with one mole of
oxygen atoms.
11. Determine the percentage composition by mass of each of the elements in
the following compounds:
(a) Calcium chloride, CaCl2
(b) Ammonium sulphate, (NH4)2SO4
(c) Sodium carbonate, Na2CO3
(d) Copper nitrate Cu (NO3)2
(H = 1, Ca = 40, Cl = 35.5, N = 14, S = 32, Na = 23, Cu = 63.5, C = 12).
12. A hydrocarbon has a percentage composition by mass of 87.80% carbon, the
rest is hydrogen. If its relative molecular mass is 82, determine the
molecular formula of the hydrocarbon.
13. A compound of carbon, hydrogen and oxygen contains 57.15% carbon,
4.76% hydrogen and the rest oxygen. If its relative molecular mass is 126,
find its molecular formula.
14. A mass of 3.6 g of magnesium reacts in excess chlorine to form a chloride.
If the mass of the chloride is 14.25 g, find the formula of the chloride
formed.
(Mg = 24, Cl = 35.5).
15. Write ionic equations for the reactions between:
(a) Aqueous solutions of sodium chloride and lead nitrate.
(b) Aqueous solutions of barium chloride and magnesium sulphate.
(c) An aqueous solution of potassium hydroxide and dilute nitric acid.
 (d) Zinc and an aqueous solution of copper(II) sulphate solution.
16. Calculate the molarity of hydroxide ions in a solution prepared by dissolving
2.8 g of sodium hydroxide in enough water to make one litre of solution.
17. What mass of copper(II) oxide will just neutralise dilute nitric acid
containing 3.15 g of pure nitric acid dissolved in water?
18. What volume of hydrogen is evolved when 20.0 g of zinc is reacted with
excess dilute sulphuric acid at s.t.p. (Zn = 65.4).
19. A 1.00 g sample of limestone was allowed to react with 100 cm3 of 0.2 M
HCl3 acid. The excess acid required 24.8 cm3 of 0.1 M NaOH solution.
Calculate the percentage of calcium carbonate in the limestone.
20. A mass of 5.125 g of washing soda crystals were dissolved and made up to
250 cm3 of solution. A 25.0 cm3 portion of the solution required 35.8 cm3 of
0.05 M sulphuric acid for neutralisation. Calculate the percentage of sodium
carbonate in the crystals.
21. What is the mass of:
(a) 22.4 litres of ammonia?
(b) 4480 dm3 of nitrogen gas? (Volume measured at s.t.p.)
22. An evacuated flask has a mass of 90.050 g. When filled with gas X, at s.t.p.
the flask weighs 90.121g. If the volume of the flask was 22.2 cm3, calculate
the relative molecular mass of gas X and suggest its identity.
23. How many molecules of gas are contained in 5.6 dm3 of nitrogen at s.t.p.?
24. Calculate the relative molecular masses of the following gases from the
information given:
(a) 0.4 g of oxygen occupies 280 cm3 at s.t.p.
(b) 700 cm3 of sulphur(IV) oxide at s.t.p weighs 2.0 g.
25. An initial volume of 80 cm3 of a mixture of propane (C3H8) gas and excess
oxygen was ignited in an experiment. The final volume was cooled and
bubbled through aqueous sodium hydroxide. The final volume was reduced
by 30 cm3.
(a) (i) What was the purpose of the NaOH solution?
(ii) Write the equation for (a) (i).
(b) Write the equation of the reaction taking place when propane is burnt in
excess oxygen.
 (c) Determine the composition of the original mixture and the volume of
residual oxygen.
26. A volume of 50 cm3 of oxygen was exploded in 50 cm3 of carbon(II) oxide.
What was the volume of the residual gas at room temperature?
27. Some 150 cm3 of nitrogen(II) oxide was completely burnt in oxygen. What
is the volume of the product formed? (All volumes measured at the same
temperature and pressure).
28. A volume of 20 litres of hydrogen chloride (HCl) was completely
decomposed to its constituent elements (hydrogen and chloride). What are
the volumes of the constituent elements?
29. In a compound of magnesium and nitrogen, 54 g of magnesium combine
with 21 g of nitrogen. Determine the empirical formula of the compound.
(Mg = 24, N = 14).
30. The composition by mass of some metal oxides is given below. Work out the
formula of each oxide:
(i) Yellow lead oxide: 4.46 g of this oxide contains 4.14 g of lead.
(ii) Red iron oxide: 6.40 g of this oxide contains 4.48 g of iron. (Fe = 56, O
= 16, Pb = 207).
31. Calculate the mass of sodium oxide, Na2O, formed when 3.45 g of sodium
burns in air. (0 = 16, Na = 23).
32. An oxide of nitrogen contains 30.43% by mass of nitrogen and has a relative
molecular mass of 92. Work out the molecular formula of the oxide. (N =
14, 0 = 16).
33. A pupil analysed a commercial vinegar solution by titration and found that
24.5 cm3 of 0.0981 M sodium hydroxide solution was required for titration
of 1 cm3 of vinegar. Calculate the molarity of ethanoic acid CH3COOH in
vinegar. (Na=23, H=1, O=16, C=12, N=14).
34. (a) What volume of acidified potassium permanganate of concentration
0.02 mol dm3 is decolourised by 200 cm3 of hydrogen peroxide of
concentration 0.02 mol dm-3? Use the following ionic equation:
2MnO-4(ag) + 6H+(ag) + 5H2O2(ag) 2Mn2+(ag) +
8H2O(l) + 5O2(l)
(b) What volume of oxygen is evolved at r.t.p.?
35. A piece of iron wire weighs 2.80 g. It is dissolved in acid, in the Fe2+ state,
 and titrated with 40.0 cm–3 of 0.200 mol dm–3 potassium chromate(VI)
solution.

Note
Both the carbonate and hydrogen
carbonate are basic to methyl orange
while only the carbonate is basic to
phenolphthalein.

What is the percentage purity of the iron wire, give the ionic equation.
6Fe2+(aq) + Cr2O2– (aq) + 14H2O(aq) 6Fe3+(aq) + 2Cr+3 (aq)+
7H2O(l)
36. What is the volume in litres for each of the following gases measured at
s.t.p.?
(a) 16 g of oxygen?
(b) 71 g of chlorine?
(c) 17.6 g of carbon(II) oxide?
37. During a practical lesson, solution X was prepared by dissolving Y g of a
mixture of sodium carbonate and sodium hydrogen carbonate in enough
distilled water and made up 500 ml of solution. About 25 cm3 of the
solution mixture was titrated with hydrochloric acid of molarity 0.1 M, first
using phenolphthalein followed by screened methyl orange as indicators.
(i) The first step of the titration using phenolphthalein indicator required
25.0 cm3 of the acid for the pink colour to be discharged and the equation
for the reaction is:
Na2CO3(aq) + HCl(aq) NaCl(aq) + NaHCO3 (aq)
(ii) The second step of the titration using screened methyl orange indicator
required 45 cm3 of the acid for the colour to turn from yellow to red
(endpoint). The following is the equation for the reaction:
NaHCO3(aq) + HCl(aq) CO2(g) + NaCl(aq) + H2O(l)
(a) Calculate I:
(i) Moles of sodium carbonate in the mixture.
(ii) Mass of the sodium carbonate in the sample mixture.
 Calculate II:
(i) Moles of sodium hydrogen carbonate in the sample.
(ii) Mass of sodium hydrogen carbonate in the sample.
(b) Mass of sample Y of the mixture.
(c) Determine the molarity of:
(i) Sodium carbonate.
(ii) Sodium hydrogen carbonate.
38. A sample of ammonium chloride was reacted with calcium hydroxide
(slaked lime) and the ammonia gas evolved was dissolved in 50.0 cm3 of
0.10 M sulphuric(VI) acid which was in excess. From the resulting solution,
25 cm3 was titrated against sodium hydroxide solution of 0.2 molar and 25.0
cm3 of the base were needed for complete neutralisation.
(a) Write balanced equations for the reactions between the:
(i) Ammonium salt and calcium hydroxide.
(ii) Ammonia gas and the acid.
(iii) Excess acid and sodium hydroxide.
(b) Determine the:
(i) Number of moles of the acid neutralised by sodium hydroxide.
(ii) Number of moles of ammonia that reacted with sulphuric(VI) acid.
(iii) Mass of the ammonia salt sample.
39. A volume of 50 cm3 of sulphur(IV) oxide was passed over heated catalyst
with 25 cm3 of oxygen. At the end of the reaction, it was found that 50 cm3
of a new oxide of sulphur had been formed, and none of the original gases
remained. Work out the formula of the new oxide.
40. A volume of 15 cm3 of ethane gas (C2H4) was exploded with 50 cm3 of
oxygen. If both volumes were measured at the same temperature, calculate
the volume of the resulting gaseous mixture.
C2H4 (g) + 3O2(g) 2CO2(g) + 2H2O(g)
What volume of oxygen was used?
41. Two gases A and B have densities of 0.09 g/cm3 and 0.16 g/cm3
respectively. If they diffuse under the same conditions, determine their
relative rates of diffusion.
42. Explain why gases are easily compressed.
43. A fixed mass of a certain gas has a volume of 76 cm3 at 37°C and 85 Kpa.
Find the volume the gas would occupy at s.t.p. (s.t.p.) conditions are 100
Kpa, 273 K).
 Chapter Organic Chemistry I
3
By the end of this chapter, the learner should be able to:

(a) Define organic chemistry.

(b) Define hydrocarbons and classify them according to their structure and
bonding.
(c) Write molecular and structural formulae of alkanes, alkenes and alkynes.
(d) Name and draw the structures of alkanes, alkenes and alkynes.
(e) Define an isomer, name and draw the structures of the isomers of
hydrocarbons with up to five carbon atoms in their molecules.
(f) Describe the general methods of preparing different hydrocarbons.
(g) Explain the gradual change in properties among the members of a
homologous series.
(h) State some uses of hydrocarbons.

Organic chemistry is the study of carbon compounds excluding the oxides of

carbon and carbonates. Carbon forms a very large number of compounds. This is
because carbon atoms form stable covalent bonds with other carbon atoms and
with atoms of other elements. This is due to the fact that carbon:
(a) Uses all its valence electrons to form four covalent bonds with carbon atoms
and with atoms of other elements.
(b) Can form single, double and triple bonds with other carbon atoms.
(c) Atoms can join each other to form long chains.
This chapter deals mainly with a group of compounds known as
hydrocarbons. Hydrocarbons are compounds which are made up of carbon and
hydrogen atoms only. They are classified into three groups depending on the
type of bond that exists between individual carbon atoms in a molecule. The
groups are alkanes, alkenes and alkynes.

Alkanes
Alkanes are a group of hydrocarbons whose carbon atoms are linked by single
covalent bonds. Hydrocarbons in which only single covalent bonds are present in
the molecules are said to be saturated.

Sources of Alkanes
Alkanes occur naturally as natural gas, biogas and in crude oil. Natural gas is a
mixture of methane, ethane, propane and butane; with methane forming 80% of
its composition. Methane forms 60 – 75% of biogas by mass, with other gaseous
alkanes forming the remaining 40 – 25%.
Crude oil is the major natural source of alkanes. It contains a range of
alkanes which can be separated into various components by fractional
distillation. This is due to the fact that the different alkanes have different boiling
points.

Experiment 3.1: How can the components of crude oil be separated?

Put about 5.0 cm3 of crude oil in a boiling tube. Add a few grains of sand or
pieces of porcelain to the crude oil to prevent bumping and breaking of the
boiling tube. Complete the set-up as shown in figure 3.1. Heat the boiling tube
gently. Collect a small amount of the first distillate at 120°C. As the temperature
rises, collect more samples of the successive distillates in clean test-tubes at
40°C intervals until a temperature of 350°C is reached.

Note:
 An ordinary thermometer of 0 – 110°C
should not be used because it will break
due to the high temperatures.

Examine the samples in terms of appearance, flammability and viscosity (how

easily they flow).
Fig. 3.1: Fractional distillation of crude oil using improvised fractionating column.

Answer the following questions

1. How did the following properties vary from the first to the last sample:
(i) Appearance?
(ii) Smell?
(iii) Flammability?
(iv) Viscosity?
(v) Boiling point?
2. What is fractional distillation?
3. Why are distillates called fractions?
4. How can the separation of the various fractions be improved?
5. What are the uses of the various fractions?

Discussion
The distillate samples collected at different temperatures have different colours
and smell. Each fraction has a different boiling point from the others. Crude oil
is a mixture of hydrocarbon molecules with different numbers of carbon atoms.
The fractions with short carbon chains have low boiling points. As the boiling
point of the fractions increase, the viscosity and the intensity of colour of the
fractions increase while flammability decreases.
The fractions obtained are not very pure because some hydrocarbons are
found in more than one fraction. Therefore, a more efficient fractionating
column can be used to improve separation. Crude oil is separated into different
components through fractional distillation. Each component separates at
different temperature at different parts of the fractionating column (see Figure
3.2). The different fractions have different uses as shown in table 3.1.
Fig. 3.2: Fractional distillation of crude oil in a refinery.

Table 3.1
 The quality of refined fuels has become a global issue. Many nations have
come together under the auspices of the United Nations Environmental
Programme and crafted the Clean Fuel Convention which seeks to have different
countries of the world commit to modernisation of their national refineries by
2006 and have them adopt cleaner low sulphur fuels. This move is aimed at
reducing emission of gases such as sulphur(IV) oxide and sulphur(VI) oxide
which pollute the air.
Cracking of Alkanes
There is usually low demand for long chain hydrocarbons, especially those with
eight or more carbon atoms in their molecules. To increase the supply of short
chain alkanes, long chain alkanes are broken up through a process called
cracking of alkanes. During the cracking process short chain alkanes, alkenes
and hydrogen are produced.
The general equation for cracking is:
Long chain alkane Smaller chain alkane + Alkenes + Hydrogen
For example, when propane is irradiated with high energy radiation, the
following reaction occurs.
There are two ways of cracking of alkanes; thermal cracking and catalytic
cracking.
Thermal cracking takes place at a very high temperature and only involves
heating the long chain alkanes. Catalytic cracking takes place at a relatively low
temperature and involves heating the long chain alkanes in the presence of a
catalyst and at low pressure. It should be noticed that cracking of petroleum is a
major source of hydrogen for industrial use such as, the manufacture of
ammonia in the Haber process.
Biomas digester
Biogas is formed when micro-organisms feed on waste organic products such as
animal dung and cellulose in the absence of oxygen resulting in decay. Biogas
contains about 60 – 75% of methane gas. In towns, the dumping sites of organic
waste produce a lot of methane gas after decomposition of the waste. Methane
gas is sometimes referred to as marsh gas. Methane gas is a very useful fuel.
Biogas digester can produce large amounts of methane gas for use as fuel in
homes. Figure 3.3 shows how biogas digester is used to obtain biogas from a
mixture of dung and other organic wastes.

Fig. 3.3: Biogas digester

Nomenclature
The names of alkanes and other organic substance follow a set system. Alkanes
have names which end with the suffix, – ane; The first four members have their
prefixes as meth-, eth-, prop - and but-. These prefixes stand for 1, 2, 3, and 4
carbon atoms in the chain respectively. However, even for members with more
than four carbon atoms, the suffix – ane is retained. The prefix numeral is used
to indicate the number of carbon atoms in the chain, e.g., pent- (5), hex- (6),
and hept- (7). The simplest alkane is methane where n = 1 and its formula is
CH4. Table 3.2 shows the names, molecular formula, structural, and skeletal
formulae of the first ten members of the alkane series.
Table 3.2: The first members of the alkane series
In the skeletal formula, only bonds between carbon atoms are shown. The bonds
are drawn in a zig-zag manner. A straight section of a zig-zag line represents a
covalent bond between two carbon atoms in the structure.
A molecular formula shows the elements present in a compound and the
proportions of their atoms in the compounds. A structural formula shows how
the atoms of the different elements are arranged in the compound. The structural
formula of a hydrocarbon can be represented as an open or condensed structural
formula.
From table 3.2, it is seen that consecutive members of the alkane series differ
by a – CH2 unit, and conform to the general formula CnH2n+2 where n is 1, 2,
3… A series such as the one of alkanes is called a homologous series. A
homologous series is a group of compounds with similar chemical properties,
chemical formulae, and they exhibit a steady gradual change in physical
properties.
The homologous series of alkanes has the following characteristics:
(i) All members conform to a general molecular formula of CnH2n+2.
(ii) All members show similar chemical properties.
(iii) The physical properties of the members change gradually along the series.
(iv) The general methods of preparation can be applied to any member of the
series.

Isomerism in Alkanes
Alkanes with more than three carbon atoms have the ability to form compounds
with the same molecular formula but different structures. The compounds
formed are called isomers. Isomers are compounds that have the same
molecular formula but different structural formulae.
The structural formula of a compound shows how the different atoms in the
molecule are arranged or joined together. The isomers of the same alkane differ
in their physical properties such as boiling points, melting points and density but
their chemical reactions are similar. If any hydrogen atom attached to an alkane
chain is removed, an alkyl group is formed. The suffix –ane in the alkane is
replaced by –yl, for example:
Alkane Alkyl group
Methane, CH4 Methyl, CH3–
 Ethane, CH3CH3 Ethyl, CH3CH2–
Butane, CH3CH2CH2CH3 Butyl, CH3CH2CH2CH2–

Methane, ethane, and propane the lowest members of the alkane series, do not
have isomers. Isomerism in alkanes starts from butane. If any hydrogen atom
attached to any middle carbon atom is replaced by an alkyl group, a branched
alkane is obtained. The naming of the branched alkane is based on the following
rules:
1. Identify the longest continuous carbon chain to determine the name of the
parent alkane. For example, in the structure,

The longest chain has four carbon atoms hence the parent name is butane.
2. Number the longest chain from the end of the chain that is near the
branching. For example, in the structure above, numbering should start from
the left, thus:

The branching is therefore on carbon 2 of the longest chain and the

substituent group is a methyl.
3. In case there are two or more similar substituent groups in the chain, they
are indicated by the prefixes; di-, tri-, tetra-, … Comas are used to separate
the numbers for example, in the following:

There are two methyl groups attached to carbon number two of the longest chain
hence, 2, 2 -dimethyl. When naming the Isomers of an alkane, the position of the
substituent group is written first followed by the name of the substituent group
and finally the name of the parent alkane.
Examples

4. When the substituent groups are a halogen and an alkyl group, the halogen
is always placed before the alkyl group. For example;

Preparation of Alkanes
In the laboratory, alkanes are prepared by the reaction between sodalime and an
appropriate alkanoate. Soda lime is a mixture of sodium hydroxide and calcium
oxide. An alkanoate is a salt of an organic acid.

Experiment 3.2(a): How is methane gas prepared in the laboratory?

Put about 5 g of sodium ethanoate and an equal mass of soda lime (mixture of
sodium hydroxide and calcium oxide) in a dry beaker. Mix them thoroughly.
Transfer the mixture into a round-bottomed flask. Set up the apparatus as shown
in figure 3.4.
Fig.3.4: Laboratory preparation of methane.

Heat the flask carefully. Collect several test-tubes of the gas. Remove the
delivery tube immediately when heating is over. Carry out the following tests on
methane and record all the observations in the table.
Table 3.3: Properties of methane

Test Observation

1. Note the colour of the gas.

2. Smell the gas by wafting it towards your nose.
3. Introduce a lighted splint at the mouth of a test-tube containing
the gas.
4. To the 4th test-tube, add about one drop of bromine liquid in a
dark place.
5. To the 5th test-tube, add about one drop of bromine liquid in a
lighted room.

Experiment 3.2(b): How is ethane prepared in the laboratory?

Put 5 g of sodium propanoate in a beaker. Add 5 g of soda lime (sodium
hydroxide + calcium oxide) to the sodium propanoate and mix thoroughly. Place
the mixture in a round-bottomed flask. Set up the apparatus as shown in figure
3.5.
Fig. 3.5: Laboratory preparation of ethane gas.

Heat the mixture in the round-bottomed flask. Collect the gas evolved over
water. When heating is over, remove the delivery tube from the water
immediately. Test the ethane gas using the tests in table 3.4. (The physical and
chemical properties of ethane are similar to those of methane. This is because
both belong to the same homologous series.)

Answer the following questions

1. Write an equation for the reaction that takes place when soda lime is
reacted with:
(a) Sodium ethanoate.
(b) Sodium propanoate.
2. Give a reason for the method used to collect the two gases.
3. Use equations to explain the observations made when a lighted wooden
splint is placed at the mouth of a test tube containing:
(a) Methane.
(b) Ethane.
4. Explain the observations made when each of the gases is mixed with:
(a) Bromine in a dark place.
(b) Bromine in the presence of sunlight.
5. What are some of the uses of:
(a) Methane
(b) Ethane

Discussion
When a mixture of sodium ethanoate and soda lime (sodium hydroxide and
calcium oxide) is heated, methane gas is obtained.

Similarly, when a mixture of sodium propanoate, and soda lime is heated ethane
gas is obtained.

In this section only the properties of methane will be discussed as a

representative of other alkanes.

Physical Properties
Methane is a non-poisonous, colourless gas. It is slightly soluble in water and
hence can be collected over water. However, it is quite soluble in organic
solvents such as ethanol and tetrachloromethane. It is less dense than air. Table
3.4 shows the physical properties of the first ten alkanes.
Table 3.4: The general physical properties of the first ten alkanes
As observed from table the 3.5 the melting and boiling points of alkanes increase
with increase in the number of carbon atoms. An increase in number of carbon
atoms results in an increase in the strength of intermolecular (van der Waals
forces). The first four straight chain alkanes are gases, the next six are liquids,
and the rest are solids. It is also observed that density increases with an increase
in molecular mass. Generally, the solubility of alkanes decreases as the
molecular size increases.
Chemical Properties
Methane burns in excess air with a pale blue flame to form carbon(IV) oxide and
water.
CH4g)+ 2O2(g) → CO2(g) + 2H2O(l)
In a limited supply of air the flame is luminous due to incomplete combustion.
CH4(g) + O2(g) → CO(g) + 2H2O(l)
Other alkanes behave in a similar manner. Methane does not react with halogens
in the dark at room temperature because there is no enough energy to split the
halogen molecules into atoms. In the presence of sunlight, methane reacts with
bromine to form bromomethane. When a substituent, like a halogen, is present in
the alkane, the resulting name must contain the halogen. The name of the
halogen becomes the prefix, and the parent alkane, the suffix. The name of the
halogen is therefore written as:

Iodo– to represent iodine.

Bromo– to represent bromine.
Chloro– to represent chlorine.
Fluoro– to represent fluorine.
Alkanes react with halogens in the presence of sunlight because the halogen
molecules are supplied with energy from light necessary to split them into atoms.
These free halogen atoms are very reactive hence they replace the hydrogen
atoms in the methane molecule. This reaction is referred to as a substitution
reaction. A substitution reaction is a reaction in which one atom or group of
atoms in a molecule is replaced by another.
Chlorine also reacts with methane in the presence of ultra violet light.
Chlorine atoms repeatedly substitute the hydrogen atoms in the methane
molecule until all the hydrogen atoms have been replaced as shown below.

If bromine is used, it likewise substitutes hydrogen but the reaction is slow. The
mixture of bromine and methane gets decolourised when left in sunlight. The
equation for the reaction of methane and bromine is:
CH4(g) + Br2(g) → CH3 Br(g) + HBr.
All the other alkanes will undergo substitution with chlorine and bromine.

Uses of Alkanes
1. Gaseous alkanes such as methane, propane, butane are used in homes as
fuels.
2. They are used in the manufacture of carbon black which is a component of
printers’ ink, and paint.
3. They are used in the manufacture of methanol, methanal, and chloromethane
which are useful industrial chemicals.
4. As a source of hydrogen during the cracking process.

Exercise 3.1
1. Name each of the following compounds:
(a) H3C—CH2—CH2—CH3

2. Give the names and molecular formula of the following.

3. Draw the structural formula for each of the following compounds:
(a) 2-methylheptane.
(b) 3-ethylhexane.
(c) 2, 2, 4-trimethylpentane.
(d) 2, 3-dichlorobutane.
4. Draw and name the structures of all the isomers of:
(a) Butane.
(b) Pentane.
(c) Hexane.
5. Distinguish between thermal and catalytic cracking of alkanes.
6. The following set up was used to prepare ethane in the laboratory.

(a) Identify a condition missing in the set up.

(b) Name substance X and write its chemical formula.
(c) Name the product produced alongside ethane in the reaction.
7. Draw and name all the possible isomers of an alkane with the molecular
formula C6H14.
8. State three uses of alkanes.
Alkenes
Alkenes are hydrocarbons which contain at least one double bond between two
carbon atoms in a molecule . The first member of the series is ethene
C2H4. because at least two carbon atoms are necessary for a double bond to be
formed. Table 3.6 gives the name, molecular formula, structural formula and
skeletal structure of the first six members of the alkene series.
Table 3.5: The First members of the alkene series

From table 3.5, it is observed that each alkene differs from the next one by a –
CH2. group, and conforms to the general formula CnH2n where n represents the
number of carbon atoms in a molecule (n = 2, 3, 4, 5…). The presence of a
double bond in alkenes results in unsaturation. The double bond in alkenes is
easily broken to accommodate more atoms. The C = C double bond determines
the chemical properties of alkenes. An atom or group of atoms such as the
which is responsible for the characteristic reactions of a compound is called a
functional group.

Nomenclature
The naming of alkenes is similar to that of alkanes. The longest straight chain in
alkenes is that which contains the C– C double bond. All alkenes have names
ending with – ene. To name them, a prefix indicating the number of carbon
atoms in the longest straight chain is followed by the suffix – ene.
Naming of alkenes is based on the following rules:
1. To determine the parent name of the alkene identify the longest carbon chain
containing the double bond.

2. Number the carbon atoms in the longest carbon chain starting from the end
nearer to the double bond. The double bond should be given the lowest
possible number.

In the two cases, the double bond is between carbon 1 and carbon 2. In
naming the lower position is used.
3. Indicate the positions of the substituent groups by showing the position of
the carbon atom to which they are attached. For example:
The structure should be:

Examples
Isomerism in Alkenes
Alkenes also show isomerism. There are two types of isomerism shown by
alkenes. These are, branching, and positional isomerism.

Branching isomerism: It occurs when a substituent group is attached to one of

the carbon atoms in the longest chain containing the double bond. For example,
the branched isomer of but-1-ene is:

Pentene has two branched isomers:

Positional isomerism: The position of the double bond in an alkene can change.
This leads to the formation of positional isomers. For example:
Experiment 3.4: How is ethene prepared in the laboratory?
Put about 20 cm3 of ethanol in a round-bottomed flask. Add pieces of broken
porcelain or sand into the flask. Place the flask in a sand bath. Set up the
apparatus as shown in figure 3.6.

Fig. 3.6: Laboratory preparation of ethene.

Note:
At a temperature of about 140°C a
different compound called ether is
predominantly formed.

Add about 40 cm3 of concentrated sulphuric acid to ethanol slowly from a

dropping funnel. The ratio of ethanol to concentrated sulphuric acid is 1:2
respectively.
Heat the mixture to a temperature of 170°C. Pass the gas evolved through
sodium hydroxide solution. Collect four test-tubes of the gas. Carry out the
following tests. Record all the observations as in table 3.6.
Table 3.6: Properties of ethane gas

Test Observation

1. Bubble ethane gas through 2 cm3 of bromine water.

2. Pass ethane gas through 2 cm3 of acidified potassium
manganate(VII).
3. Pass ethane gas through 2 cm3 of acidified potassium
 chromate(VI).
4. Smell the gas by wafting it towards the nose.
5. Note the colour of the gas.
6. Introduce a lighted wooden splint at the mouth of a test-tube
containing the gas.

Alternative Method for Preparing Ethene Gas

Soak a piece of glass wool in ethanol. Place the cotton wool in a boiling tube and
clamp the boiling tube in a horizontal position. Place some aluminium oxide in a
porcelain boat in the tube. Set the apparatus as shown in figure 3.7.

Fig. 3.7: Laboratory preparation of ethene.

Heat the aluminium oxide strongly. Some heat is then conducted to the ethanol
in the cotton wool which then vapourises it.

Answer the following questions

1. Write an equation for the reaction between ethanol and concentrated
sulphuric acid.
2. Explain the observations made when ethene gas was bubbled through:
(i) Bromine water.
(ii) Acidified potassium manganate(VII).
(iii) Acidified potassium Chromate(VI).
(Use chemical equations in all cases.)
3. Write an equation for the reaction that takes place when a burning splint is
introduced at the mouth of a test-tube containing the gas.
4. What is the purpose of the broken porcelain in the reaction flask?
 5. Why was sodium hydroxide solution used in the experiment?
6. What property of ethene gas enables one to use the above method of
collecting it?
7. Why is it preferable to use a sand bath instead of heating the round-
bottomed flask directly.

Discussion
When a mixture of ethanol and concentrated sulphuric(VI) acid is heated at
temperatures between 160°C and 180°C, water is removed from ethanol and
ethene gas is formed.

The removal of water molecules from ethanol is a dehydration process. Conc.

sulphuric acid is a dehydrating agent. Broken porcelain or sand is used to
prevent bumping which may result in cracking of the flask.
The gas produced is passed through sodium hydroxide to remove
sulphur(IV) oxide and carbon(IV) oxide which are formed when concentrated
sulphuric acid and ethanol decompose respectively due to heat. Ethene can also
be prepared by dehydration of ethanol using aluminium oxide.

The aluminium oxide acts both as a catalyst as well as a dehydrating agent.

Physical Properties
Ethene is a colourless and oduorless gas. It is slightly soluble in water hence is
collected over water. The solubility of alkenes decreases with increase in
molecular mass. Ethene is very soluble in organic solvents such as
methylbenzene, and tetrachloromethane. The melting point, and boiling points of
alkenes generally increase with increase in the number of carbon atoms due to an
increase in inter-molecular forces, hence, high boiling and melting points. Table
3.7 shows melting, boiling points, and density of some of the alkenes.
Table 3.7: Physical properties of the first five alkenes
Chemical Properties
Alkenes are more reactive than alkanes due to the presence of the double bond.
The double bond is the reactive site of alkenes.

(a) Combustion
All alkanes burn in air with a yellow sooty flame unlike alkanes. This is because
they are unsaturated. They have a higher carbon to hydrogen ratio than alkanes.
Since alkenes burn with a sooty flame, they are not preferred for use as fuels.
Equation for the combustion
C2H4(g) + 3O2(g) → 2CO2(g) + 2H2O(T)

(i) Addition reactions

Ethene undergoes addition reactions because of the double bond. An addition
reaction is one in which one molecule adds to another to form a single product.

(a) Halogenation
This is the addition of halogen atoms across a double bond. Chlorine and
bromine are decolourised immediately when ethene is added. Equations for the
reactions are:
(iii) When bromine is dissolved in water, and reacted with ethene, the following
reaction takes place:

Bromine water is decolourised. This is a test for alkenes.

(b) Hydrohalogenation
Addition of hydrogen halides such as hydrogen bromide, and hydrogen chloride
is as shown:

(c) Hydrogenation
Hydrogen gas reacts with ethene at high temperature in the presence of
palladium or nickel catalyst to form ethane.
When hydrogen gas is passed through liquid vegetable and animal oil heated to a
temperature of 180°C, in the presence of a nickel catalyst, solid fat is formed.
Therefore this process of hydrogenation is used in the manufacture of margarine
to make the oils solid.

(ii) Self-addition reaction

Ethene molecules have the ability to react with each other to form a larger
molecule which has a higher molecular mass. Each molecule of ethene is known
as a monomer. When many monomers are joined together, they form a polymer.
The following equation shows how a polymer is formed:

The process in which several monomers combine to form a polymer is referred

to as polymerisation.
When ethene molecules join with each other this way, they form a polymer
known as polyethene. This polymerisation process can be represented by a
general equation;

Where n = 2, 3, 4, 5..

(iii) Addition reactions with oxidising agents

(a) Potassium manganate(VII), KMnO4

When ethene is bubbled into acidified potassium manganate(VII) solution, the
colour of the solution turns from purple to colourless. The manganate(VII) is an
oxidising agent and it adds oxygen at the double bond. The manganate(VII) ion
is reduced to manganese(II) ions and water.
This is also another test for alkenes. The equation is:

(b) Acidified potassium chromate(VI) (K4Cr2O7)

When the potassium dichromate(VI) is used in the reaction the orange colour of
the chromate(VI) changes to green. Potassium chromate(VI) acts as an oxidising
agent adding oxygen at the double bond. The chromate(VI) ions are reduced to
chromium(III) ions(Cr3+).

(c) Reaction with concentrated sulphuric acid

Ethene reacts with concentrated sulphuric acid at room temperature to form ethyl
hydrogen sulphate.

When ethyl hydrogen sulphate is added to water, and warmed, the product
formed is ethanol.

Ethyl hydrogen sulphate is hydrolysed to ethanol. This process is referred to as

hydrolysis. Hydrolysis is the reaction of a compound with water such that the
hydroxyl group of the water remains intact. Generally, the hydrogen atom is
added first to ethene molecule to break the double bond, then the hydroxyl group
is added.

Tests for Alkenes

The addition reactions of alkenes with bromine water, acidified potassium
manganate (VII) or acidified potassium(VI) dichromate can be used to test for
the presence of a double bond.

Uses of Alkenes
1. In the manufacture of plastics.
2. In the manufacture of ethanol through hydrolysis reactions.
3. In the ripening of fruits (ethene).
4. In the manufacture of detergents.
5. In the laboratory preparation of ethan –1,2 –diol (glycol) which is used as in
coolant (especially as an engine coolant).

Exercise 3.2
1. Name the following compounds:
(a) H3C – CH= CH – CH3
(b) H2C = CH – CH2 – CH2 – CH3
(c) H2C = CH – CH = CH – CH3
(d) H2C = CH – CH = CBr – CH3
2. Draw the structural formula of the following compounds:
(a) 2–methylpent – 2–ene.
(b) 3–methylbut–1–ene.
(c) 1–chloro – 2 –methylpentane.
(d) 1 – bromo – 3 – ethylpentene.
3. Define the following terms:
(a) monomer.
(b) polymer.
4. Alkenes undergo hydrogenation to form alkanes as shown by the following
equation;

Identify catalyst x and condition y.

5. State four uses of alkenes.
6. State a chemical test carried out to show evidence for the unsaturation in
hydrocarbons.
7. The following structure represents part of a polymer. Given that the
molecular mass of the monomer is 76.5. Answer the questions below.

(a) Identify and draw the structure of the repeat unit.

(b) Name the monomer.
(c) Write the molecular formula of the monomer.
8. The following equation represents the reaction for the preparation of ethene
from ethanol;

(a) Name reagent A.

(b) Name the process by which ethene is produced in the reaction
represented by the equation.

Alkynes
Alkynes are hydrocarbons which contain a carbon – carbon triple bond (–C≡C–)
in the molecule. Table 3.8 shows the name, molecular formula, structural
formula, and skeletal structure of the first six members of the series.
Table 3.8: physical properties of the first five alkynes
From table 3.8, it is observed that each alkyne differs from the next by a –CH2
group and conforms to the general formula, CnH2n-2, where 'n' represents the
number of carbon atoms in a molecule, (n = 2, 3, 4…). The first alkyne member
is n = 2 because at least two carbon atoms are necessary for the formation of a
triple bond. The presence of the triple bond results in unsaturation.

Nomenclature
The naming of alkynes is similar to that of alkenes. All alkynes have names
ending in –yne. To name them, a prefix indicating the number of carbon atoms in
the longest straight chain is followed by the suffix –yne. The longest continuous
carbon chain must contain the carbon-carbon triple bonds. This chain is
numbered such that the carbon atoms having the triple bond have the lowest
possible value as shown in the examples below.
Isomerism in Alkynes
Alkynes show branching isomerism, and positional isomerism.

(a) Branching Isomerism

This occurs when a substituent group is attached to the longest chain containing
the carbon - carbon triple bond.

For example the branched isomer of pent-l-yne is:

(b) Positional Isomerism

The position of the triple bond in an alkyne molecule can change. This results in
the formation of two or more compounds with the same molecular formula but
different structural formula.
For example:
Ethyne and propyne do not show positional isomerism.

Experiment 3.5: How is ethyne prepared in the laboratory?

Place sand into a flat bottomed flask enough to cover the base. Place a small
amount of calcium carbide (CaC2) on the sand.

Fig: 3.8: Laboratory preparation of ethyne

Add water from a dropping funnel drop-wise until a steady flow of the gas is
obtained. Collect the gas in several test tubes, and carry out the following tests.
Record all the observations as in table 3.9.
Table 3.9: Properties of ethyne gas

Test Observation
(a) Smell the gas by wafting it towards the nose.
(b) Note the colour of the gas.
(c) Place a burning splint at the mouth of a test-tube
containing the gas.
(d) Add 1 cm3 of bromine water to the gas in a test-tube, and
shake the mixture.
(e) Add 11 cm3 of acidified potassium manganate(VII) to the
 gas in a test-tube Shake the mixture.
(f) Add 1 cm3 of acidified potassium dichromate(VI) to the
gas in a test-tube. Shake the mixture.

Answer the following questions

1. Write the equation for the reaction between calcium carbide and water.
2. Write the equations for:
(i) Burning ethyne in air.
(ii) Reaction of ethyne and bromine water.
3. Why is it necessary to dry the flask at the beginning of the experiment.
4. What is the function of the sand in the flask.

Discussion
Calcium carbide reacts with water at room temperature to form ethyne and
calcium hydroxide.
CaC2(s) + 2H2O(l) → C2H2(g) + Ca(OH)2(aq)
A layer of sand is placed at the base of the flask because the reaction is
highly exothermic. The sand absorbs the excess heat and therefore prevents the
flask from breaking. The flask must be dry before the start of the experiment to
avoid formation of the gas before the set-up is complete.

Physical Properties
Ethyne is a colourless gas and has a pleasant smell when pure. It is slightly
soluble in water, and therefore can be collected over water. The solubility of
alkynes is higher in non-polar solvents.
Table 3.10: Some physical properties of alkynes
Alkynes with lower molecular mass are gases at room temperature. While those
with a higher molecular mass are solids.

Chemical Properties
Ethyne burns in air, and also undergoes addition reactions.

(a) Combustion Reactions

Ethyne like any other hydrocarbon will burn in air to form an oxide of carbon,
and water. This reaction is usually accompanied by production of a lot of heat,
therefore, it is preferably used in oxy-acetylene flames. In a limited supply of air,
ethyne undergoes incomplete combustion to form a mixture of carbon and
carbon(II) oxide. The yellow sooty flame observed is due to the unburnt carbon.

In excess air, ethyne burns completely to form carbon(IV) oxide and water.

(b) Addition Reactions

Addition reactions in alkynes are faster than in alkenes due to the presence of the
triple bond.

(i) Reaction with hydrogen (hydrogenation)

Ethyne reacts with hydrogen in the presence of a nickel catalyst to form first
ethene, then ethane.
(ii) Reaction with halogens (halogenation)
When ethyne reacts with red-brown bromine vapour, the bromine vapour is
decolourised. The decolourisation process is faster in ethyne than in ethene. The
bromine atoms are added to the carbon-carbon triple bond to form 1, 1, 2, 2,-
tetrabromoethane. This reaction takes place at room temperature and it is a two-
step reaction. Thus:

Pure chlorine reacts with ethyne with a violent explosion forming carbon, and
hydrogen chloride.
C2H2 + Cl2(g) → 2C(s) + 2HCl(g)
When diluted with an inert gas, chlorine reacts with ethyne to from 1, 1, 2, 2-
tetrachloroethane in a two step reaction.
(iii) Reaction with hydrogen halides (Hydrohalogenation)
Ethyne does not react with all the hydrogen halides. Hydrogen iodide reacts
readily at room temperature, hydrogen bromide reacts when warmed while
hydrogen chloride reacts slowly.

(ii) Hydrogen bromide reacts with ethyne to produce 1,1–dibromoethane

(CH3CHBr2)

(iii) The reaction between hydrogen chloride gas is slow.

Test for Alkynes

The test for an alkynes is similar to the tests for alkenes in which the oxidising
agents are decolourised. However, the reaction is faster in alkynes than in
alkenes.

Uses of Alkynes
1. They are used in the industrial manufacture of compounds such as
adhesives, and plastics.
2. In the manufacture of synthetic fibres such as rayon.
3. In the production of important chemical reagents and solvents, in which it is
used as a starting material.
4. They are used in the oxy-acetylene flame which is used for welding, and
 cutting metals.

Exercise 3.3
1. (a) Write the molecular formula of butyne.
(b) Draw the open structural formula of butyne.
(c) Butyne burns with a yellow sooty flame in a limited supply of air.
Explain.
(d) Write the equation for the reaction in (c).
2. Name the compound represented by the following structure.

3. Draw the open structure of the compound with the following molecular
structure: C6H10
4. The reaction between bromine vapour and ethyne is faster than with ethene.
Explain.

Summary
1. Organic chemistry is the study of carbon compounds excluding the oxides of
carbon and carbonates.
2. Hydrocarbons are organic compounds composed of carbon, and hydrogen
only.
3. The compounds of a particular homologous series have the same general
formula, functional group and chemical properties but their physical
properties may vary.
4. Alkanes have a general formula CnH2n+2. They occur naturally in crude oil.
They are generally unreactive because they are saturated. However, they
normally undergo combustion, and substitution reactions under certain
conditions.
5. Alkenes have the general formula CnH2n. They are unsaturated and have at
least a carbon-carbon double bond (– C = C –). They undergo combustion
and addition reactions.
6. Alkynes have a general formula CnH2n–2. They have at least a carbon-carbon
 triple bond. They are more unsaturated and more reactive than alkenes.

Revision Exercise
1. Crude oil is the main source of organic compounds such as hydrocarbons.
The hydrocarbons in the crude oil have to be separated.
(a) Name four important hydrocarbons obtained from crude oil.
(b) Give the uses of the four hydrocarbons named in (a) above.
(c) Explain with the help of a suitable diagram, the principles used in
separating hydrocarbons in crude oil.
2. What do you understand by the following terms:
(a) Catalytic cracking.
(b) Thermal cracking.
3. Study the following reaction scheme and answer the questions that follow:

(a) Name:
(i) Colourless gas A.
(ii) Product B.
(iii) Gas D.
(iv) Liquid E.
(b) Write balanced equations for each of the reactions forming the products
in (a).
(c) Name the type of reactions taking place in Step I and II.
(d) State the importance of the reaction taking place in Step II.
4. Explain why an organic compound with formula C3H6 burns with a more
sooty flame than C3H8
5. Butane and bromine react as shown below:
CH3,CH2.CH2CH3 + Br2 → CH3CH2.CH2Br + HBr
(a) Name the type of reaction taking place in the equation above.
(b) State the condition under which the above reaction takes place. Explain.
6. A hydrocarbon Q, was found to decolourise potassium manganate(VII)
solution. When two moles of Q are burnt completely, six moles of
carbon(IV) oxide and six moles of water were formed.
(a) Write the structural formula of Q.
(b) Name the homologous series to which Q belongs.
(c) Name one industrial source of Q.
7. The diagram below shows the combustion of ethane gas.

(a) Identify substance x.

(b) Write the equation for the complete combustion of ethane gas.
(c) What is the purpose of ice cold water in the experiment?
(d) The pH of substance X was found to be less than 7. Explain this
observation.
8. One mole of hydrogen bromide reacts with an organic compound N to give
a single product with the structural formula shown below:

(a) Give the name of the hydrocarbon.

(b) Draw the possible structure of N.
 Chapter Nitrogen And
4 Its Compounds

By the end of the chapter the learner should be able to:

(a) Describe how nitrogen is isolated from air.

(b) Describe how nitrogen is prepared in the laboratory and state its
properties and uses.
(c) Describe the laboratory preparation and state the properties and uses of
the oxides of nitrogen.
(d) Describe the laboratory preparation of ammonia and state its properties
and uses.
(e) Explain the differences in chemical reactions of ammonia gas and its
aqueous solution.
(f) Describe the industrial manufacture of ammonia.
(g) Calculate the percentage of nitrogen in nitrogen containing fertilisers.
(h) Describe the laboratory preparation and manufacture of nitric(V) acid and
state its uses.
(i) Explain the reactions of both dilute and concentrated nitric(V) acid.
(j) Identify the products formed when different nitrates are heated.
(k) State and explain the pollution effect of nitrogen compounds in the
environment.

Nitrogen is a non metal in group V of the periodic table. It has an atomic number
of seven and has an electron arrangement of 2.5. Nitrogen exists in air as a
gaseous element consisting of diatomic molecules. About 78% by volume of the
atmosphere is composed of nitrogen making it the most important source of
nitrogen.
Nitrogen also occurs combined in compounds such as sodium nitrate,
potassium nitrate and proteins.

Isolation of Nitrogen from Air

In the laboratory, nitrogen is isolated from air by first passing the air through
concentrated potassium hydroxide or sodium hydroxide which absorbs
carbon(IV) oxide.
KOH(aq) + CO2(g) KHCO3(aq)
The remaining part of air is then passed over heated copper turnings to
remove oxygen.
2Cu(s) + O2(g) 2CuO(s)
The residual gas is then collected as shown in figure 4.1.

Fig. 4.1: Laboratory isolation of nitrogen gas from air.

The nitrogen so obtained contains noble gases as impurities. Nitrogen is

obtained on a large scale by fractional distillation of liquid air. Dust particles are
first removed from air through electrostatic precipitation. The dust-free air is
then passed through concentrated sodium hydroxide solution to remove
carbon(IV) oxide gas. The remaining air is passed into a condensation chamber
and cooled to –25°C. Water vapour separates out as ice. The residual gas is
compressed to a pressure of 200 atmospheres.
Repeated expansion and contraction of the air cools it to a liquid at a
temperature of –200°C. The main constituents of liquid air at this stage are
nitrogen and oxygen whose boiling points are –196°C and –183°C respectively.
Nitrogen has a lower boiling point and therefore distills out first followed by
oxygen. The flow chart in figure 4.2 summarises the major steps in the isolation
of nitrogen.
Fig 4.2: Summary of fractional distillation of air.

Experiment 4.1: How is nitrogen prepared in the laboratory?

Mix 7 g of sodium nitrite and 5.5 g of ammonium chloride. Place the mixture in
a round-bottomed flask. Add 150 cm3 of water and set the apparatus as shown in
figure 4.2. Heat the flask gently and collect two gas jars and six test-tubes of the
gas.

Fig. 4.2: Preparation of nitrogen in the laboratory.

Carry out the following tests on nitrogen gas and record your observations in
table 4.1.
Table 4.1: Properties of nitrogen gas.
 Test Observation

(a) Observe the colour of the gas.

(b) Smell the gas by wafting the gas towards your nose with
your hand.
(c) Insert a burning splint into a test-tube of the gas.

(d) Insert pieces of red and blue litmus paper in a test-tube of

gas.
(e) Add a few drops of lime water into a test-tube of the gas.

(f) Lower a piece of burning magnesium on a deflagrating

spoon into a gas jar of nitrogen.
(g) Repeat test (f) using sulphur.

Answer the following questions

1. State and explain:
(a) The observations made when a mixture of sodium nitrite and
ammonium chloride is heated.
(b) The method of collection of nitrogen.
2. Explain why the nitrogen obtained from this method has a lower density
than the one isolated from air.
3. Write an equation for the reaction between:
(i) Sodium nitrite and ammonium chloride.
(ii) Magnesium and nitrogen.

Discussion
Ammonium chloride and sodium nitrite react to form ammonium nitrite and
sodium chloride.
NaNO2(aq) + NH4Cl(aq) NH4NO2(aq) + NaCl(aq)
 Ammonium nitrite is unstable and decomposes to form nitrogen and steam.
NH4NO2(aq) N2(g) + 2H2O(g)
Nitrogen obtained from this reaction is less dense than that isolated from air
because it does not contain impurities.
Nitrogen is a colourless, oduorless and tasteless gas that is slightly less dense
than air. The boiling point is –96°C. It is slightly soluble in water. Nitrogen
neither burns nor supports combustion. It is neutral and has no effect on moist
litmus paper and does not react readily with other elements. However at higher
temperatures, it reacts with metals in group I and II to form their nitrides.
3Mg(s) + N2(g) Mg3N2(s)
When some water is added to the nitride, ammonia gas and magnesium
hydroxide are formed.
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(aq) + 2NH3(g)
Nitrogen gas does not react with sulphur and phosphorus. It is chemically
unreactive under ordinary conditions. A molecule of nitrogen has a triple
covalent bond, N≡N, which is very strong and requires a lot of energy to break.
The presence of nitrogen in the air slows down the rate of burning due to its inert
nature.
Nitrogen is distinguished from other gases by its negative results with all the
tests used to identify common gases.

Uses of Nitrogen
• Manufacture of ammonia in the Haber process.
• In light bulbs because of its inert nature it cannot react with the hot filament
of the bulb.
• As a refrigerant, e.g., in the storage of semen for artificial insemination.

Exercises 4.1
1. (a) The apparatus shown in the diagram below was used by a student to
obtain dry nitrogen from air. Study it and answer the questions that
follow.
(i) Name liquid:
(I) A
(II) B
(ii) Write down the observation made in the combustion tube.
(iii) Write an equation for the reaction taking place in tube Q.
(iv) Name one impurity in the nitrogen gas collected.
(v) Another student replaced the copper metal with magnesium
turnings. Explain why a lower yield of nitrogen was obtained in the
syringe.
(b) Fractional distillation of liquid air produces nitrogen and oxygen as the
major products. Describe how nitrogen gas is obtained from the liquid air.
(Boiling points N2 = –196°C, O2= –183°C)
2. Explain why nitrogen is unreactive at low temperatures.
3. Name any three uses of nitrogen.

Oxides of Nitrogen
Several oxides of nitrogen exist. These include:
1. Nitrogen(I) oxide N2O.
2. Nitrogen(II) oxide NO.
3. Nitrogen(IV) oxide, NO2.

Nitrogen(I) oxide (Dinitrogen oxide)

Experiment 4.2: How is nitrogen(I) oxide prepared?
Place about four spatulafuls of ammonium nitrate in a flask and set up the
apparatus as shown in figure 4.3. Heat the flask gently and collect several jars of
the gas produced over water.

Caution:
Stop heating while some ammonium
nitrate still remains in the flask to avoid
an explosion.

Fig. 4.3: Laboratory preparation of nitrogen(I) oxide.

Carry out the tests in table 4.2 on nitrogen(I) oxide and record your observations.
Table 4.2: Properties of nitrogen(I) oxide

Test Observation

1. Note the colour of the gas.

2. Smell the gas by wafting it towards your nose.

3. Lower pieces of moist red and blue litmus papers into a

test-tube of the gas.
4. Insert a glowing splint into a test-tube containing the gas.

5. Pass a stream of nitrogen(I) oxide gas over heated copper as

shown in figure 4.5. Test the gas collected using a burning
splint, moist litmus paper and lime water.
Fig. 4.4: Reaction of nitrogen(I) oxide with copper.

Answer the following questions

1. Explain the observations made in the combustion tube.
2. Write an equation for the formation of nitrogen(I) oxide from ammonium
nitrate.
3. Name the products formed when the nitrogen(I) oxide is passed over
heated copper.
Discussion
Ammonium nitrate melts and decomposes on heating to form nitrogen(I) oxide
and steam.
NH4NO3(s) N2O(g) + 2H2O(g)
Nitrogen(I) oxide is a colourless gas with a pleasant smell. The gas causes
insensitivity when inhaled. It is slightly less dense than air. It is fairly soluble in
cold water but insoluble in warm water. For this reason it is usually collected
over warm water.
Nitrogen(I) oxide gas is not reactive at room temperature. However it
relights a glowing splint. The heat from the glowing splint dissociates the gas
producing nitrogen and oxygen gas. The oxygen produced relights the splint.
When nitrogen(I) oxide is passed over heated copper, a black residue of
copper (II) oxide and nitrogen are formed.
Cu(s) + N2O(g) CuO(s) + N2(g)
Sulphur burns brilliantly in nitrogen(I) oxide to form sulphur(IV) oxide and
nitrogen.
 S(s) + N2O(g) SO(s) + N2(g)

Uses of Nitrogen(I) Oxide

• It was formerly used as an anaesthetic during dental surgery. Patients
recovering from it laugh hysterically hence the name ‘laughing gas’.
• It is used as a food additive.
• It is used as an oxidiser in racing car engines and rockets.
• It is used to produce flames for analytical work.

Nitrogen(II) Oxide (Nitrogen Monoxide)

Experiment 4.3: How is nitrogen(II) oxide prepared?
Place a few pieces of copper turnings in a conical flask and set up the apparatus
as shown in figure 4.5. Add dilute nitric acid (1 volume of concentrated nitric
acid mixed with 1 volume of water) to the copper turnings. Collect eight test-
tubes and two gas jars of the gas.

Fig. 4.5: Laboratory preparation of nitrogen(II) oxide.

Carry out the following tests on nitrogen(II) oxide and record your observations
in table 4.3.
Table 4.3: Properties of nitrogen(II) oxide

Test Observation

1. Note the appearance of the gas.

2. Lower a burning splint into the gas.

 3. Drop a piece of wet litmus paper into the gas.

4. Lower a piece of burning magnesium in a deflagrating

spoon into a gas jar full of the gas.
5. Repeat test (4) above using phosphorus.

6. Bubble the gas through a cold solution of iron(II) sulphate.

7. Open a test-tube of the gas in air.

Answer the following questions

1. Write an equation for the formation of nitrogen(II) oxide from the reaction
of copper turnings and dilute nitric acid.
2. Explain the presence of the brown fumes in the flask.
3. What are the products formed when burning:
(i) Magnesium was lowered into the gas?
(ii) Phosphorus was lowered into the gas?

Discussion
Nitrogen(II) oxide is produced when copper and dilute nitric(V) acid react.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 4H2O(1) + 2NO(g)
Nitrogen(II) oxide is oxidised by oxygen in the flask to form red-brown
fumes of nitrogen(IV) oxide.
2NO(g) + O2 (g) 2NO2 (g)
The fumes gradually disappear as the air in the flask is exhausted.
Nitrogen(IV) oxide formed dissolves in the water in the trough. Nitrogen(II)
oxide is a colourless gas. It is slightly soluble in water and has no effect on moist
litmus paper.
Nitrogen(II) oxide neither burns nor supports combustion. However it
oxidises some strongly heated elements to their oxides. Magnesium continues to
burn in nitrogen(II) oxide. The heat produced decomposes the gas into nitrogen
and oxygen. The oxygen produced enables the hot element to continue burning.
 2Mg(s) + 2NO(g) 2MgO(s) + N2(g)
2Cu(s) + 2NO(g) 2CuO(s) + N2(g)
P4(s) + 10NO(g) 2P2O5(g) 5N2(g)
Iron(II) sulphate solution turns dark brown when nitrogen(II) oxide is
bubbled through it. This is due to the formation of iron(II) sulphate – nitrogen(II)
oxide complex, FeSO4.NO.

When exposed to air, nitrogen(II) oxide is readily oxidised by oxygen to

form red brown fumes of nitrogen(IV) oxide. This reaction is used as the test for
nitrogen(II) oxide.

Nitrogen(IV) Oxide (Nitrogen Dioxide)

Experiment 4.4: How is nitrogen(IV) oxide prepared?
Place some copper turnings in a conical flask. Set the apparatus as shown in
figure 4.6. Add concentrated nitric acid to the copper turnings. Collect two gas
jars and one test-tube of the gas.

Caution:
Nitrogen(IV) oxide is poisonous and
should therefore be prepared in a fume
chamber or in the open.
Fig. 4.6: Laboratory preparation of nitrogen(IV) oxide.

Carry out the following tests on nitrogen (IV) oxide and record your
observations in table 4.4.
Table 4.4: Properties of nitrogen(IV) oxide

Test Observation

1. Note the colour of the gas.

2. Bubble some of the gas formed through distilled water

containing litmus paper.
3. Bubble the gas through sodium hydroxide solution. Test the
resulting solution with litmus paper.
4. Cool one of the test-tubes containing the gas in an ice-cold
mixture and warm.
5. Using a pair of tongs, lower a piece of burning magnesium
ribbon into a gas jar full of the gas.
6. Using a pair of tongs, lower a piece of burning phosphorus
into a gas jar full of the gas.

Answer the following questions

1. State and explain what is observed when concentrated nitric(V) acid is
added to copper turnings.
 2. Write equations for the following reactions:
(i) Nitrogen(IV) oxide and water.
(ii) Magnesium and nitrogen(IV) oxide.
(iii) Phosphorus and nitrogen(IV) oxide.
3. Explain the observation made when nitrogen(IV) oxide is cooled and then
warmed.

Discussion
When concentrated nitric(V) acid is added to copper turnings, a vigorous
reaction takes place and red-brown fumes of nitrogen(IV) oxide are evolved.
Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)
Nitrogen(IV) oxide may also be prepared by thermal decomposition of
nitrates of metals below sodium in the reactivity series.
However, lead(II) nitrate is the most suitable because it is not hydrated.
When heated, lead(II) nitrate decomposes to form lead(II) oxide, nitrogen(IV)
oxide and oxygen. The set up below can be used to prepare nitrogen(IV) oxide
from metal nitrates.

Fig. 4.7: Preparation of nitrogen(IV) oxide gas.

2Pb(NO3)2(s) 2PbO(s) + 4NO2(g) + O2(g)

The gases produced are passed through a U-tube surrounded by ice-cold
water. On cooling, nitrogen(IV) oxide condenses to form dinitrogen tetraoxide,
N2O4, which is a pale-yellow liquid. Oxygen gas is collected over water.

Nitrogen(IV) oxide gas is easily liquefied. At room temperature nitrogen(IV)

oxide collected exists as an equilibrium mixture of itself and dinitrogen
tetraoxide.

When heated, nitrogen(IV) oxide dissociates to form a colourless mixture of

nitrogen (II) oxide and oxygen.

Nitrogen(IV) oxide is a reddish-brown gas, with an irritating pungent smell.

The gas is poisonous. It is denser than air and is therefore collected by
downward delivery. Nitrogen(IV) oxide is soluble in water. It dissolves in water
to form both nitric(III) acid and nitric(V) acid.
2NO2(g)+ H2O(l) HNO2(aq) + HNO3(aq)
It neutralises alkalis forming a mixture of their corresponding nitrates and
nitrites. Magnesium ribbon continues to burn in nitrogen(IV) oxide to form
white fumes of magnesium oxide and nitrogen.
4Mg(s) + 2NO2(g) 4MgO(s) + N2(g)
Burning phosphorus continues to burn in nitrogen(IV) oxide to form
phosphorus (V) oxide.
2P4(s) + 10NO2(g) 4P2O5(g) + 5N2(g)
The heat produced by the burning element decomposes nitrogen(IV) into
nitrogen and oxygen. Oxygen liberated combines with the hot element.

Uses of Nitrogen(IV) Oxide

• In the manufacture of nitric(V) acid.
• As an intermediate in the manufacture of explosives, nylon and plastics.
• As an oxidising agent in the lead chamber during the manufacture of
sulphuric (VI) acid.

Exercise 4.2
1. State and explain the observations made when;
 (a) A gas jar containing nitrogen(II) oxide is exposed to air.
(b) Nitrogen(II) oxide gas is bubbled through freshly prepared and
acidified iron(II) sulphate solution.
(c) Concentrated nitric(V) acid is added to copper turnings.
(d) A sample of nitrogen(IV) oxide in a test-tube is cooled in ice-cold
water.
2. A student set up the apparatus below in an attempt to prepare and collect
nitrogen (IV) oxide gas. Study the set up and answer the questions that
follow.

(a) (i) Identify one mistake in the set up.

(ii) Write the equation to show the effect of heat on silver nitrate.
(b) Another student decided to use solid sodium nitrate in place of silver
nitrate.
Write an equation to show the effect of heat on sodium nitrate.
3. (a) A piece of burning magnesium was lowered into a gas jar containing
nitrogen(I) oxide. State and explain the observation made.
(b) Write an equation for the reaction in (a) above.
4. One of the pollutants from the exhaust fumes of vehicles is nitrogen(IV)
oxide. Explain how nitrogen(IV) oxide is produced from the internal
combustion engines.
5. A stream of dry nitrogen(II) oxide is passed over heated zinc powder in a
combustion tube as shown.
(i) State the observations made in the combustion tube.
(ii) Name gas R.
(iii) Write an equation for the reaction to show the formation of gas R.
6. Both nitrogen(I) oxide and nitrogen(II) oxide are colourless gases. Describe
how the two gases can be distinguished from each other.
7. Nitrogen(IV) oxide gas is bubbled into a solution of sodium hydroxide.
Identify all the products formed.

Ammonia
Ammonia, NH3, is a compound of nitrogen and hydrogen. It is a gas at room
temperature.

Experiment 4.5: How is ammonia prepared in the laboratory?

Mix calcium hydroxide (slaked lime) with ammonium chloride. Place the
mixture in a round-bottomed flask. Arrange the apparatus as shown in figure 4.8.
Heat the mixture gently and collect one gas jar and three test-tubes of ammonia
gas.
Fig. 4.8: Preparation of ammonia.

Perform the following tests outlined in table 4.5 and record your observations as
shown in the table.
Table 4.5: Properties of ammonia.

Test Observation

1. Observe the colour of the gas.

2. Smell the gas by wafting it towards your nose.

3. Insert a burning splint in a gas jar full of the gas.

4. Place a glass rod dipped in concentrated hydrochloric acid at

the mouth of a test-tube full of the gas.

Answer the following questions

1. Why is the reaction flask set in a slanting position?
2. How would you tell when a gas jar is full of the gas?
3. Write equations for the reactions between:
(a) Ammonium chloride and calcium hydroxide.
(b) Hydrochloric acid and ammonia.

Discussion
Ammonia is prepared in the laboratory by heating a mixture of an ammonium
salt and an alkali. Ammonia is a more volatile base and is displaced by a less
volatile base, e.g., NaOH, KOH and Ca(OH)2.
When a mixture of ammonium chloride and calcium hydroxide is heated,
ammonia gas is produced. The flask containing the mixture is set in a slanting
position to prevent water which condenses on the cooler parts of the apparatus,
from running back into the flask and causing it to crack.
Ca(OH2)(s) + 2NH4Cl(s) CaCl2(s) + 2H2O(l) + 2NH3(g)
The ionic equation for the reaction is:

A moist litmus paper placed at the mouth of the gas jar turns blue indicating
the gas jar is full of ammonia. Calcium oxide (quicklime) is used as a drying
agent. This is because ammonia reacts with the other common drying agents.
Concentrated sulphuric(VI) acid reacts with ammonia to form ammonium
sulphate.
2NH3(g) + H2SO4(l) (NH4)2SO4(aq)
Calcium chloride forms a complex compound with ammonia.
CaCl2(s) + 4NH3(g) CaCl2.4NH3(s)
Ammonia is a colourless gas, with a characteristic choking pungent smell. It
is less dense than air and therefore it is collected by upward delivery. The gas is
very soluble in water.
Ammonia turns moist red litmus paper blue showing that it is alkaline. This
is the confirmatory test for ammonia. When a glass rod dipped in concentrated
hydrochloric acid is brought to the mouth of a gas jar full of ammonia, hydrogen
chloride fumes react with ammonia to form white fumes of ammonium chloride.
NH3(g) + HCl(g) NH4Cl(g)

Experiment 4.6: How is an aqueous solution of ammonia prepared?

Place a mixture of calcium hydroxide and ammonium chloride in a boiling tube.
Set the apparatus as shown in figure 4.9. Gently heat the mixture.
Fig. 4.9: Preparation of aqueous ammonia.

Answer the following questions

1. Why is a funnel used when dissolving ammonia?
2. Which ion is responsible for the alkaline nature of ammonia solution?
Discussion
Ammonia dissolves in water to form an alkaline solution. A little of the
dissolved gas combines with water to form ammonium ions and hydroxide ions.

The hydroxide ion, OH–, gives the solution its alkaline properties. A funnel is
used to prevent the water from ‘sucking back’ into the flask by providing a large
surface area for absorption of ammonia.

Experiment 4.7: How soluble is ammonia in water?

Collect dry ammonia gas in a round-bottomed flask and set up the apparatus as
shown in figure 4.10. Open the clip and let the water rise up the tube. Close the
clip when the water reaches the tip of the tube. Open the clip again after a while
and observe what happens.

Note:
It is important in the fountain
 experiment to dry the gas and collect it
in a dry flask. Allow a little water into
the flask first, close the tap or clip and
wait for a while, then open the clip to
allow more water to flow in freely in a
fountain.

Fig. 4.10: Solubility of ammonia in water.

Answer the following questions

1. What observations were made when the clip was opened the second time?
Explain.
2. What does this experiment show about the solubility of ammonia in water?

Discussion
When a drop of water gets to the jet, it dissolves a lot of the ammonia gas in the
flask creating a partial vacuum. When the clip is opened the second time, the
water is forced into the flask by the atmospheric pressure leading to the
formation of a fountain. This experiment illustrates the high solubility of
ammonia gas in water. Universal indicator is added to enhance the visibility of
the “fountain”.

Experiment 4.8: What happens when aqueous ammonia is added to

solutions containing metal ions?
Place about 2 cm3 of solutions containing ions of calcium, magnesium,
aluminium, zinc, iron, lead and copper in separate test-tubes. To each solution
add aqueous ammonia drop by drop. Shake the mixture after each drop.
Continue adding aqueous ammonia until it is in excess. Record your
observations in table 4.6.
Table 4.6: Reaction of ammonia with metal ions

Metal ion in Few drops of aqueous Excess aqueous

solution ammonia ammonia

Ca2+

Mg2+

Al3+

Zn2+

Fe2+

Fe3+

Pb2+

Cu2+

Answer the following questions

1. State and explain the observations made when a few drops and then excess
aqueous ammonia are added to each of the solutions containing metal ions
listed in table 4.6.
2. Write ionic equations for the reactions that take place when a few drops of
aqueous ammonia are added to the metal ion.
3. Which metal ions reacted differently with excess aqueous ammonia? Write
equations for the changes that occur.
Discussion
Table 4.7 summarises the observations made when aqueous ammonia is added to
solutions containing metal ions.
Table 4.7: Summary of reactions of aqueous ammonia with metal ions

Metal ion in Few drops of Excess aqueous ammonia

solution aqueous ammonia
Ca2+ No white precipitate No white precipitate
Mg2+ White precipitate White precipitate does not dissolve.
AP+ White precipitate White precipitate does not dissolve.
Zn2+ White precipitate White precipitate dissolves to form a
colourless solution.
Fe2+ Green precipitate Green precipitate does not dissolve.
Fe3+ Brown Precipitate Brown precipitate does not dissolve.
Pb2+ White precipitate White precipitate does not dissolve.
Cu2+ Pale-blue precipitate Pale-blue precipitate dissolves to
form a deep-blue solution.

Aqueous ammonia precipitates many metal hydroxides from solutions

containing ions of the metal. Aqueous ammonia is a weak alkali and will not
precipitate the hydroxide in water if it is slightly soluble, for example, calcium
hydroxide. Ionic equations representing precipitation of insoluble metal
hydroxides are:

Note:
Calcium ions form a white precipitate
when 2 M aqueous ammonia is used.

Mg2+(aq) + 2OH-(aq) Mg(OH)2(s)

 White precipitate
Al3+(aq)+ 3OH-(aq) Al(OH)3(s)
White precipitate
Zn2+(aq) + 2OH-(aq) Zn(OH)2(s)
White precipitate
Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)
Green precipitate
Fe3+(aq)+ 3OH-(aq) Fe(OH)3(s)
Red brown precipitate
Pb2+(aq) + 2OH-(aq) Pb(OH)2(s)
White precipitate
Cu2+(aq) + 2OH-(aq) Cu(OH)2(s)
Pale-blue precipitate

Zinc hydroxide and copper(II) hydroxide dissolve in excess ammonia due to the
formation of complex ions.

Experiment 4.9: How does aqueous ammonia react with dilute

acids?
Place about 2 cm3 of 1 M sulphuric acid, 2 M hydrochloric acid and 2 M nitric
acid in three different test-tubes. Add two drops of methyl orange to each test-
tube. Add aqueous ammonia drop-wise to each test-tube until a yellow colour
persists. Record your observations.

Answer the following questions

1. What type of reaction takes place between aqueous ammonia and dilute
 acids?
2. Write the equation for the reaction between aqueous ammonia and dilute:
(i) Sulphuric acid.
(ii) Hydrochloric acid.
(iii) Nitric acid.
Discussion
Ammonia gas dissolves in water to form aqueous ammonia. Some of the
dissolved ammonia molecules react with water molecules to form ammonium
hydroxide.
NH3(aq) + H2O(l) → NH4OH(aq)

Therefore, aqueous ammonia neutralises acids to form ammonium salts and

water.
2NH4OH(aq) + H2SO4(aq) → (NH4)2SO4(aq)+ H2O(l)
NH4OH(aq) + HCl(aq) → NH4Cl(aq)+ H2O(l)
NH4OH(aq)+ HNO3(aq) → NH4NO3(aq) + H2O(l)
If dry ammonia is bubbled through dilute acids, ammonium salts are formed.
2NH3(g) + H2SO4(aq) → (NH4)2SO4(aq)
NH3(g) + HCl(aq) → NH4Cl(aq)
NH3(g) + HNO3(aq) → NH4NO3(aq)

Experiment 4.10: Does ammonia burn in air?

Set up the apparatus as shown in figure 4.11. Carry out the following tests and
record your observations in the format shown in table 4.8.
Fig. 4.11: Burning ammonia in air.
Table 4.8: Reactions of ammonia

Test Observation

(a) Pass dry ammonia into the glass tube and

light the gas at the jet.
(b) Pass oxygen into the glass tube for a short
time. Pass dry ammonia gas into the glass
tube. Insert a lighted splint into the mixture.

Answer the following questions

1. What conditions are necessary for ammonia to burn?
2. Name the products formed when ammonia burns in oxygen.
3. Write an equation for the burning of ammonia.

Discussion
Ammonia does not burn in air. However, it burns with a greenish-yellow flame
in air enriched with oxygen to form nitrogen and steam.
4NH2(g) + 3Oz(g) 2N2(g) + 6H2O(g)

Experiment 4.11: How does ammonia react with air in the presence
of a platinum wire?
Place concentrated ammonia solution in a conical flask. Arrange the apparatus as
shown in figure 4.12. Heat a platinum wire until it is red-hot. Pass oxygen or air
through the concentrated ammonia. Place the hot platinum or copper in the flask.
Record your observations.
Fig. 4.12: Catalytic oxidation of ammonia using platinum wire.

Note:
In the absence of a platinum wire a
copper wire can be used.

Answer the following questions

1. What was observed when a hot platinum coil was lowered into the conical
flask?
2. Write an equation for the reaction that took place.
3. Why does the platinum wire continue to glow even after heating has
stopped?
4. What is the purpose of using platinum wire in this reaction?

Discussion
The hot platinum wire glows on coming into contact with the fumes of ammonia
from the concentrated ammonia solution. Ammonia and oxygen react on the
surface of the platinum which acts as a catalyst. A lot of heat is produced during
the reaction that enables the platinum coil to continue glowing. Ammonia is
oxidised to nitrogen(II) oxide in the presence of a platinum catalyst.
 Reddish-brown fumes of nitrogen (IV) oxide are produced due to further
oxidation of nitrogen (II) oxide.
2NO(g)+ O2(g) 2NO2(g)

Experiment 4.12: How does ammonia react with copper(II) oxide?

Place copper(II) oxide in a combustion tube. Arrange the apparatus as shown in
the figure 4.13. Heat the oxide strongly and pass a stream of ammonia gas over
it. Carry out the tests outlined in table 4.9. using the products formed.

Fig. 4.13: Reaction of ammonia with copper (II) oxide.

Table 4.9: Reaction of ammonia with copper

Test Observation

(a) Test the colourless liquid collected in the U-tube with

cobalt(II) chloride paper.
(b) Test the gas formed with:
(i) A burning splint.

(ii) A moist litmus paper.

(iii) Lime water.

Answer the following questions

1. Explain the observations made in the combustion tube.
 2. State the reducing agent in this reaction.
3. Name the products formed when ammonia reacts with hot copper(II)
oxide.
4. Write the equation for the reaction between ammonia and copper(II) oxide.

Discussion
When ammonia is passed over heated copper(II) oxide, the black copper(II)
oxide turns into a brown solid as copper(II) oxide is reduced to copper metal by
ammonia.

Note:
Lead(II) oxide or iron(II) oxide can be
used in place of copper(II) oxide.

The colourless liquid collected in the U-tube turns cobalt(II) chloride paper pink.
This test confirms the presence of water. The gas collected has no effect on a
moist litmus paper and lime water. It extinguishes a burning splint. The gas is
nitrogen.

Large Scale Manufacture of Ammonia, the Haber Process

Ammonia is prepared on a large scale by the Haber Process. The raw materials
for the process are nitrogen and hydrogen. Nitrogen is obtained by the fractional
distillation of liquid air. Hydrogen is obtained from natural gas or as a by-
product of cracking long chain alkanes.
Nitrogen and hydrogen gases are mixed in the ratio of 1:3 and passed
through a purifier to remove impurities which would otherwise poison the
catalyst. The impurities removed are; carbon(IV) oxide, sulphur(IV) oxide and
dust particles.
The mixture of nitrogen and hydrogen is then compressed to between 200
and 500 atmospheres and passed into a catalytic chamber maintained at
temperatures of between 400°C and 500°C. Iron is used as the catalyst. The
reaction is highly exothermic and sustains the temperature in the catalytic
chamber.
N2(g) + 3H2(g) 2NH3(g) + Heat
The hot mixture of ammonia and gases which have not reacted are passed
into the heat exchanger where cooling takes place. The heat is used to heat the
incoming mixture of nitrogen and hydrogen, this makes the process economical.
The ammonia produced is liquefied in the condenser and stored in cylinders.
The gases which have not reacted are recycled therefore reducing wastage. The
flow chart in figure 4.14 summarises the major steps in the manufacture of
ammonia.

Fig. 4.14: Summary of steps involved in the large scale manufacture of ammonia.

The yield of ammonia is high at higher pressures and low temperature.

However it is expensive to maintain higher pressure. At low temperatures the
reaction is slow. To reduce the production cost optimum conditions of 500°C,
200 atmospheres and iron catalyst are employed.
Uses of Ammonia
• As a fertiliser.
• Manufacture of nitrogenous fertilisers.
• As a refrigerant, e.g., in large scale refrigerating plants such as ships and
warehouses.
• Softening water.
• Removal of greasy stains.
• Manufacture of hydrazine that is used as rocket fuel.
Nitrogenous Fertilisers
Nitrogen is the most important nutritional element required by plants. There
several nitrogen containing fertilisers which are manufactured and sold in
various brand names. These include:

(i) Ammonium sulphate, (NH4)2SO4

It is the most widely used nitrogenous fertiliser. It is prepared by reacting
ammonia and sulphuric acid.
2NH3(g) + H2SO4(aq) (NH4)2SO4(s)
The percentage of nitrogen in ammonium sulphate fertilisers is
determined as follows.

(ii) Ammonium nitrate, NH4NO3

It is used widely due to a high content of nitrogen. It is prepared by
neutralising nitric acid with ammonia.
NH3(aq) + HNO3(aq) NH4NO3(aq)
The percentage composition of nitrogen in ammonium nitrate is determined
as:

(iii) Ammonium phosphate (NH4)3PO4

Apart from nitrogen, ammonium phosphate also contains phosphorus which
is of vital importance for plant growth. It is prepared by neutralising
phosphoric acid with ammonia.
3NH3(g) + H3PO4(aq) (NH4)3 PO4(aq)
(iv) Urea (NH2)2 CO
Urea is prepared by passing carbon(IV) oxide through ammonia solution.
CO2(g)+ 2NH3(aq) CO(NH2)2(aq) + H2O(l)

Percentage of nitrogen in urea

(v) Calcium ammonium nitrate (CAN)

Calcium ammonium nitrate is a mixture of ammonium nitrate and calcium
nitrate.
The percentage composition of nitrogen in calcium ammonium nitrate is
about 27%.
From the examples given, urea is a better nitrogenous fertiliser because it
contains a higher content of nitrogen.

Some nitrogenous fertilisers used by farmers

Excersice 4.3
1. A colourless gas was passed over heated lead(II) oxide and the products of
the reaction were collected as shown in the diagram.
 (a) Name gas x.
(b) State the observation made in the combustion tube.
(c) Write an equation for the reaction that takes place in the combustion
tube.
(d) Why is it possible to collect nitrogen gas a shown in the set up?
(e) Nitrogen gas can be obtained either from reduction of ammonia gas or
from air. State giving reasons which of the two sources you would
recommend to an industrialist.
2. A student set up the apparatus shown in the following diagram to prepare a
solution of ammonia gas in water.

State three mistakes the student made, and suggest corrections.

3. The gases methylamine (CH5N) and ammonia (NH3) are closely related
compounds and have similar properties. Each can be represented by the
formula R—NH2.

(a) State what R will be in the case of:

(i) ammonia.
(ii) methylamine.
 (b) Predict the effect of methylamine on:
(i) water coloured with litmus solution.
(ii) hydrogen chloride gas.
4. When excess ammonia solution is added to a solution of zinc ions, a
colourless solution forms. Write the formula of the complex ions formed.
5. The diagram below shows the heating of ammonium chloride.

The moist red litmus paper first changed to blue then red. Explain these
observations.

Nitric(V)Acid
Experiment 4.13: How is nitric(V) acid prepared in the laboratory?
Place about 10 g of potassium nitrate in a retort flask. Carefully, add
concentrated sulphuric(VI) acid to completely cover the potassium nitrate.
Assemble the apparatus as shown in figure 4.17. Heat gently. Cool the fumes
produced with cold running water. Collect condensed nitric(V) acid as shown in
figure 4.15.
 Note:
The apparatus used is all glass as
nitric(V) acid attacks rubber and cork
connections. Heating should be as
gentle as possible to minimise thermal
decomposition of nitric(V) acid.

Fig. 4.15: Laboratory preparation of nitric(V) acid

Answer the following questions

1. What is observed when a mixture of potassium nitrate and concentrated
sulphuric(VI) acid is heated?
2. Write an equation for the reaction that takes place.
3. What is the colour of condensed nitric(V) acid? Explain.

Discussion
Nitric(V) acid is prepared by reacting concentrated sulphuric(VI) acid with a
nitrate. Potassium nitrate is commonly used as it does not contain water of
crystallisation. When a mixture of potassium nitrate and concentrated
sulphuric(IV) acid is heated, fumes of nitric(V) acid are produced. Nitric(V) acid
is more volatile and is readily displaced from nitrates by the less volatile
sulphuric(VI) acid.
KNO3(s) + H2SO4(l) KHSO4(s) + HNO3(aq)
The nitric(V) acid fumes are brown due to the presence of nitrogen(IV) oxide.
The nitrogen(IV) oxide is formed by thermal decomposition of nitric(IV) acid.

The nitric(V) acid collected is yellow in colour. This is due to the presence of
dissolved nitrogen(IV) oxide. The yellow colour can be removed by bubbling air
through the acid.
The acid salt, KHSO4 is formed during the preparation of the nitric(V) acid
instead of the normal salt, K2SO4. The normal salt is not formed because it
requires high temperatures that cannot be achieved in a classroom situation.
Industrial Manufacture of Nitric(V) Acid
Nitric(V) acid is manufactured by a process that relies on the catalytic oxidation
of ammonia. The raw materials for this process are ammonia, air and water. The
flow chart in figure 4.16. summarises the major steps in the process.

Fig. 4.16: Industrial manufacture of nitric(V) acid.

A mixture of ammonia and air is first purified to remove dust particles and other
impurities that would otherwise ‘poison’ the catalyst. The mixture is then
compressed to a pressure of 9 atmospheres and passed on to the catalytic
chamber via the heat exchanger.
As it passes through the heat exchanger, the temperature of the ammonia-air
mixture rises to 230°C. In the catalytic chamber, the temperature of the mixture
is raised further to 900°C. It is then passed over a platinum-rhodium catalyst.
The ammonia combines with oxygen to form nitrogen(II) oxide. The reaction is
highly exothermic.
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
The hot gaseous products from the catalytic chamber are cooled in the heat
exchanger. Nitrogen(II) oxide is mixed with more air and is oxidised to
nitrogen(IV) oxide.
2NO(g) + O2(g) 2NO2(g)
This reaction is carried out at a temperature of below 45°C to ensure a high
yield of nitrogen(IV) oxide. The mixture of nitrogen(IV) oxide, air and
unreacted nitrogen(II) oxide is passed up the absorption tower against a
downward flow of hot water. Nitrogen(IV) oxide and water combine to form
nitric(V) acid and nitric(III) acid (nitrous acid).

The nitric(III) acid formed is oxidised to nitric(V) acid by excess air.

The mixture that results is 65% nitric(V) acid and 35% water. A more
concentrated acid may be obtained by careful distillation of the solution over
phosphorus(V) oxide or concentrated sulphuric(VI) acid that acts as a
dehydrating agent. Concentrated nitric(V) acid is a colourless fuming liquid with
a boiling point of 83°C. Commercial nitric(V) acid is 68% pure and has a density
of 1.42 g/cm3.

Reactions of Dilute Nitric(V) Acid

Experiment 4.14: How does nitric(V) acid react with metals?
Place a piece of clean magnesium ribbon (about 2 cm) in a clean test-tube. Add
dilute nitric(V) acid and observe. Test any gas produced using a burning splint.
Repeat the procedure using zinc and copper in place of magnesium. Record your
observations in table 4.10.
Table 4.10: Reaction of dilute nitric(V) acid with metals

Metal Observations

Magnesium

Zinc

Copper

Answer the following questions

 1. State and explain the observations made during the course of the
experiments.
2. Write equations for the reaction between dilute nitric(V) acid and:
(a) Magnesium.
(b) Zinc.
(c) Copper.
Discussion
Dilute acids usually react with metals higher in the reactivity series to liberate
hydrogen gas. However, dilute nitric(V) acid does not produce hydrogen with
some metals as expected. This is because any hydrogen produced is at once
oxidised by the nitric(V) acid to water. The acid is reduced to one or more of the
oxides of nitrogen.
Very dilute nitric(V) acid has little oxidising power and magnesium will displace
hydrogen from it.
Mg(s) + 2HNO3(aq) Mg(NO3)2(aq) + H2(g)
With zinc, no hydrogen is produced as the hydrogen is immediately oxidised to
water. The acid is reduced to nitrogen(II) oxide.
3Zn(s) + 8HNO3(aq) 3Zn(NO3)2(aq) + 4H2O(l) + 2NO(g)
The nitrogen(II) oxide is colourless but on exposure to air it is oxidised to red-
brown nitrogen(IV) oxide.

Dilute acids do not react with metals below hydrogen in the reactivity series.
However a 50% dilute nitric(V) acid does not behave like a typical acid because
it reacts with copper to produce copper(II) nitrate, nitrogen(II) oxide and water.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 2NO(g) + H2O(l)

Experiment 4.15: How does dilute nitric(V) acid react with

carbonates?
Place a spatulaful of sodium carbonate in a clean test-tube. Add dilute nitric
acid. Test the gas evolved. Repeat the procedure using calcium carbonate, zinc
carbonate, copper(II) carbonate and sodium hydrogen carbonate in place of
sodium carbonate. Record your observations in table 4.11.
Table 4.11: Reaction of dilute nitric(V) acid with carbonates

Carbonate or hydrogen carbonate Observation

Sodium carbonate

Zinc(II) carbonate

Copper carbonate

Sodium hydrogen carbonate

Answer the following questions

Write equations for the reaction between nitric(V) acid and:
(a) Sodium carbonate.
(b) Zinc carbonate.
(c) Copper(II) carbonate.
(d) Sodium hydrogen carbonate.

Discussion
Dilute nitric(V) acid behaves like a 'typical' acid by reacting with carbonates and
hydrogen carbonates to produce a nitrate, carbon(IV) oxide and water.
Na2CO3(s) + 2HNO3(aq) 2NaNO3(aq) + CO2(g)+ H2O(l)
ZnCO3(s) + 2HNO3(aq) Zn(NO3)2(aq) + CO2(g) + H2O(l)
CuCO3(s) + 2HNO3(aq) Cu(NO3)2(aq) + CO2(g) + H2O(l)
NaHCO3(s) + HNO3(aq) NaNO3(aq) + CO2(g) + 2H2O(l)

Experiment 4.16: How does dilute nitric(V) acid react with metal
hydroxides and oxides?
Put 2 cm3 of 2 M nitric(V) acid solution in a clean test-tube. Slowly, add 2 M
sodium hydroxide to which universal indicator has been added. Repeat the
experiment using a spatulaful of calcium oxide, copper(II) oxide and lead(II)
oxide in place of sodium hydroxide. Warm if necessary. Record your
observations in table 4.12.
Table 4.12: Reaction of dilute nitric (V) acid with metal hydroxides and oxides

Hydroxide or oxide Observation

Sodium hydroxide

Calcium oxide

Copper(II) oxide

Lead(II) oxide

Answer the following question

Write equations for the reaction between nitric(V) acid and:
(a) Sodium hydroxide solution.
(b) Calcium oxide.
(c) Copper(II) oxide.
(d) Leads(II) oxide.

Discussion
Metal hydroxides and oxides are neutralised by dilute nitric (V) acid to form a
metallic nitrate and water only.

Reactions of Concentrated Nitric(V) Acid

Experiment 4.17: How does concentrated nitric(V) acid react with
iron(II) sulphate, sulphur and copper?
Perform the experiments outlined in table 4.12 and record your observations.
Table 4.12: Reactions of concentrated nitric(V) acid

Experiment Observations

1. Add 2 cm3 of acidified iron(II) sulphate into a clean test-

tube. Add a little concentrated nitric acid and warm the
mixture.
2. Place a spatulaful of sulphur in a clean test-tube. Add 2 cm3
of concentrated nitric(V) acid. Warm the mixture.
3. Place a few pieces of copper turnings in a clean test-tube.
Add 2 cm3 of concentrated nitric(V) acid.

Answer the following questions

1. Explain the observations made when concentrated nitric(V) acid is added
to:
(i) Iron(II) sulphate solution and the mixture warmed.
(ii) Sulphur, and the mixture warmed.
(iii) Copper turnings.
2. Write equations for the reaction between concentrated nitric(V) acid and:
(i) Acidified iron(II) sulphate.
(ii) Sulphur.
(iii) Copper.

Discussion
Concentrated nitric(V) acid is a powerful oxidising agent. It oxidises iron(II)
salts to iron(III) salts and is itself reduced to nitrogen(II) oxide. The pale-green
iron(II) sulphate solution is oxidised to yellow iron(III) sulphate.
6FeSO4(aq) + 3H2SO4(aq) + 2HNO3(l) 3Fe2(SO4)3 (aq) + 2NO(g) +
4 H2O(l)
 Nitrogen(II) oxide is colourless. As it moves up the test-tube it is quickly
oxidised by oxygen in the air to red-brown fumes of nitrogen(IV) oxide.

Fig. 4.19: Reactions of nitric(V) acid with FeSO4(aq).

Hot concentrated nitric(V) acid oxidises sulphur to sulphuric(VI) acid and water
while it is reduced to nitrogen(IV) oxide.
S(s) + 6HNO3(aq) H2SO4(aq) + 6NO2(g) 2H2O(l)
Copper is oxidised to copper(II) nitrate as the nitric(V) acid is reduced to water
and nitrogen(IV) oxide.
3Cu(s) + 8HNO3(aq) 3Cu(NO3)2(aq) + 4H2O(l) + 2NO2(g)

Uses of Nitric(V) Acid

• Manufacture of fertilisers, e.g., ammonium nitrate.
• Manufacture of explosives, e.g., Trinitrotoluene.
• Manufacture of dyes and drugs.
• Purification of metals such as silver and gold.
• Etching designs on some metals.

Nitrates
Nitrates are salts that are derived from nitric(V) acid. They are usually prepared
by the action of dilute nitric(V) acid on either a base or a carbonate. Some
nitrates can be obtained by direct reaction of a metal with concentrated nitric(V)
acid.

Action of Heat on Nitrates

Experiment 4.18: What is the effect of heat on nitrates?
Add one spatulaful of potassium nitrate into a clean dry test-tube. Heat gently
and then strongly. Keep on testing for any gas produced using a glowing splint.
Repeat the experiment using sodium nitrate, zinc nitrate, copper(II) nitrate and
ammonium nitrate. Record your observations as in table 4.13.
Table 4.13: Effect of heat on nitrates

Nitrate Observation on heating Observation on cooling

Sodium nitrate

Zinc nitrate

Copper(II) nitrate

Ammonium nitrate

Answer the following questions

1. State and explain the observations made when each of the nitrates is
heated.
2. How does the ease of decomposition of metal nitrates relate to the activity
series of metals.

Discussion
Hydrated metallic nitrates produce water vapour when gently heated. On strong
heating, they all decompose. Sodium nitrate and potassium nitrate melt and
decompose on strong heating to produce oxygen gas and the nitrite of the metal.
2NaNO3(s) 2NaNO2(s) + O2(g)
KNO3(s) KNO2(s) + O2(g)
Nitrates of metals below sodium up to copper in the reactivity series
decompose on heating to give the metal oxide, nitrogen(IV) oxide and oxygen.
Thus:
 Note:
when lead(II) nitrate is heated a
cracking sound is produced. The
cracking sound is due to the air trapped
inside the crystal which on expansion
causes the crystals to burst producing
the sound.

Nitrates of metals below copper decompose on heating to produce the metal,

nitrogen(IV) oxide and oxygen. For example silver nitrate decomposes to
produce silver, nitrogen(IV) oxide and oxygen gas.
2AgNO3(s) 2Ag(s) + 2NO2(g) + O2(g)
The ease with which metal nitrates decompose increases down the reactivity
series of the metals.
Ammonium nitrate when heated decomposes to nitrogen(I) oxide and water.
NH4NO3(s) N2O(g) + 2H2O(g)
Dry nitrogen(I) oxide relights a glowing splint. However the steam produced
does not allow a glowing splint to relight.

Test for Nitrates

Experiment 4.19: What is the test for nitrates?
Carry out the tests outlined in table 4.14 and record your observations.
Table 4.14: Test for nitrates
 Test Observation

1. Place one spatulaful of sodium nitrate into a clean test-tube.

Add 2 cm3 of distilled water and shake the mixture. Add 1
cm3 of freshly prepared iron (II) sulphate and shake the
mixture again. Add concentrated sulphuric acid slowly and
carefully along the wall of the test-tube as shown in figure
2.22.
2. Place a spatulaful of sodium nitrate in a dry test-tube. Add a
few drops of concentrated sulphuric acid. Warm the mixture
and add a few pieces of copper turnings.

Fig. 4.17: Testing for nitrate ions.

Answer the following questions

1. Explain what happens when concentrated sulphuric acid is added to the
mixture of sodium nitrate and iron(II) sulphate solution.
2. Write equations for the reactions taking place in:
(a) Experiment 1.
(b) Experiment 2.

Discussion
When concentrated sulphuric acid is added to the mixture of sodium nitrate and
iron (II) sulphate solution, the acid sinks to the bottom. This is because the acid
is denser that the solution. The reaction produces heat. A brown ring is formed at
the junction of the two layers. The brown ring is due to the formation of iron(II)
sulphate–nitrogen (II) oxide complex, FeSO4.NO.
All nitrates give the same result; hence this reaction is referred to as the
brown ring test for nitrates. This is a confirmatory test for nitrates.
A safer method of testing for the presence of nitrate ions is by warming a
mixture of concentrated sulphuric(VI) acid and the suspected nitrate in the
presence of copper turnings.
When sodium nitrate is mixed with concentrated sulphuric acid and the
mixture warmed in the presence of copper turnings, brown fumes of
nitrogen(IV) oxide are produced. This reaction takes place in two stages.
NaNO3(s) + H2SO4(l) NaHSO4(s) + HNO3(l)
Cu(s) + 4HNO3(l) Cu(NO3)2(aq) + 2H2O(l) + 2NO2(g)

Pollution Effects of Nitrogen Compounds in the Atmosphere

Oxides of nitrogen such as nitrogen(II) oxide and nitrogen(IV) oxide are
atmospheric pollutants. Nitrogen(II) oxide is produced in internal combustion
engines when nitrogen and oxygen from the air combine at high temperatures.
N2(g) + O2(g) 2NO(g)
In the atmosphere, nitrogen(II) oxide is quickly oxidised to nitrogen(IV)
oxide.
2NO(g) + O2(g) 2NO2(g)
The nitrogen(IV) oxide reacts with water in the atmosphere to produce
nitric(III) and nitric(V) acids.

The nitric(III) acid is further oxidised to nitric(V) acid.

2HNO2(aq) + O2(g) 2HNO3(aq)
The nitric(V) acid eventually reaches the ground as acid rain. Acid rain
causes the loss of chlorophyll (chlorosis) from plant leaves. This leads to the
death of the affected plants.
Acid rain also corrodes stone buildings and metallic structures thereby
weakening them and destroying their beauty. Rainwater containing dissolved
nitric(V) acid leaches vital minerals from soils. These are converted into soluble
nitrates and washed away from the top soil. This leads to poor crop yields.
Nitrogen(IV) oxide undergoes chemical reactions in the air to produce one of
the major components of smog. Smog reduces visibility for motorists, irritates
the eyes and causes breathing problems.
When nitrate ions from nitrogen containing fertilisers find their way into
water bodies they encourage rapid growth of algae. This eventually leads to the
reduction in the oxygen content in the water. As a result, aquatic animals such as
fish die.
The presence of nitrate ions in drinking water may also cause ill health to
humans. This is because in the body, the nitrate ions are converted into
carcinogenic compounds.

Reducing Environmental Pollution by Nitrogen Compounds

There is an urgent need to reduce environmental pollution. Some of the measures
that can be taken to reduce environmental pollution by nitrogen compounds
include:
(a) Recycling unreacted gases in the manufacture of nitric acid to prevent
release into the environment.
(b) Treating sewage and industrial effluents to remove nitrogen compounds
before releasing them into rivers and lakes.
(c) Fitting the exhaust systems of vehicles with catalytic converters which
convert nitrogen oxides into harmless nitrogen gas.
(d) Adding lime to lakes and soils in the surrounding regions to reduce acidity.
(e) Applying fertilisers at the right time and in the correct proportion to prevent
them from being washed into water masses.

Exercise 4.4
1. When hot concentrated nitric(V) acid is added to sulphur, a redish-brown
gas and a colourless liquid are formed.
(i) Write an equation for the reaction.
(ii) Identify the oxidising agent in the reaction above.
2. Explain the following:
 (a) No hydrogen gas is produced when zinc metal reacts with dilute
nitric(V) acid.
(b) A yellow solution is formed when hot concentrated nitric(V) acid is
added to pale-green iron(II) sulphate.
3. The following set-up is used to prepare nitric(V) acid in the laboratory.

(a) All the apparatus used during preparation of nitric(V) acid are made of
glass. Give a reason.
(b) Name solid K.
(c) Give a reason why it is possible to separate nitric(V) acid from the
sulphuric(VI) acid used as one of the reagents.
(d) Give one use of nitric(V) acid.
4. Use the flow chart drawn to answer the questions that follow.
 (a) Name:
(i) Substance C.
(ii) Compound K.
(iii) The deep-blue solution.
(b) Write the formula of compound K and the deep-blue solution.
5. NH4NO3 was gently heated and the products collected as shown in the
diagram.

State one chemical and one physical test that can be used to identify gas X.
6. Nitrogen(II) oxide and nitrogen(IV) oxide are some of the gases released
from car exhaust pipes. Explain how these gases affect the environment.
Summary
1. Nitrogen is the most abundant gas in the earth’s atmosphere.
2. Nitrogen is an unreactive gas.
3. Ammonia is produced on a large scale by the Haber process.
4. Ammonia is the only common alkaline gas.
5. Nitric(V) acid is manufactured by the catalytic oxidation of ammonia.
6. Nitric(V) acid is a strong oxidising agent.
7. Dilute nitric(V) acid does not produce hydrogen when reacted with metals
except with magnesium.
8. All nitrates decompose on heating. The nitrates of potassium and sodium
decompose to the metal nitrite and oxygen. Nitrates of metals below copper
in the activity series of metals decompose to metal, nitrogen(IV) oxide and
oxygen. All other metal nitrates decompose to metal oxide, nitrogen(IV)
oxide and oxygen. Ammonium nitrate decomposes to nitrogen(I) oxide and
water.
9. Some oxides of nitrogen are atmospheric pollutants.

Revision Exercise
1. When compound X is heated, a red-brown gas is evolved and a yellow
residue is left on cooling. Name:
(i) The red-brown gas.
(ii) The ions present in the residue.
(iii) Compound X.
2. Dry ammonia gas is passed over heated lead(II) oxide in a combustion tube
as shown in the diagram.
 (a) What observations would be made in the combustion tube?
(b) Outline a chemical test you would use to identify the colourless liquid
collected in the U-tube.
(c) Name the colourless gas.
(d) Write an equation for the reaction between ammonia and lead(II) oxide.
(e) State one industrial use of ammonia.
3. Explain the following:
(a) Nitric(V) acid is usually kept in dark-brown bottles.
(b) Nitric(V) acid is often yellow in colour.
4. Aqueous ammonia was added to copper(II) sulphate solution drop wise until
in excess.
(a) What observations were made?
(b) Write down the ionic equations representing the observations
mentioned in (a).
5. Calculate the volume of oxygen that would be obtained from the
decomposition of 21.25 g of sodium nitrate at s.t.p. (1 mole of a gas
occupies 22.4 dm3 at s.t.p.) (N = 14, Na = 23, O = 16).
6. What would be observed if the following tests were carried out on iron(II)
sulphate solution:
(a) A little aqueous ammonia is added to iron(II) sulphate solution.
(b) A few drops of concentrated nitric acid are added to iron(II) sulphate
solution and warmed gently.
(c) Excess aqueous ammonia is added dropwise to the mixture in (a) above.
7. The reaction scheme shown below outlines a method for preparation of
fertilisers.
 (a) Name the substances A, B, C, D, E, F and G.
8. The set-up below was used to study the reaction between ammonia and air
in the presence of a platinum catalyst.
(a) The platinum wire continues to glow without further heating. Explain.
(b) Brown fumes are observed in the flask. Explain.
(c) Write equations for the reactions representing:
(i) Catalytic oxidation of ammonia.
(ii) The formation of the brown fumes.

9. What is the importance of the element nitrogen in the atmosphere?

10. Give the effects of using ammonia directly in the soil.
 Chapter Sulphur And
5 Its Compounds

By the end of the Chapter, the learner should be able to:

(a) Name the sources of sulphur.

(b) Describe the extraction of sulphur.
(c) Describe the preparation of the allotropes of sulphur.
(d) State the properties and uses of sulphur.
(e) Name and describe the preparation of the oxides of sulphur.
(f) State the properties and uses of the oxides of sulphur.
(g) Describe the contact process for the manufacture of sulphuric acid.
(h) Describe the properties and state the uses of sulphuric acid.
(i) Describe the preparation and state the properties of hydrogen sulphide.
(j) Explain pollution effects of sulphur containing compounds.

Sulphur is the second member of group VI elements. It is placed just below

oxygen in the periodic table. It has an atomic number 16 hence its electron
arrangement is 2.8.6.
Sulphur occurs naturally as an element in deposits in places such as Texas
and Louisiana in U.S.A, Sicily in Italy, and various places in Japan.
Sulphur also occurs in combination with other elements as sulphides and
sulphates. The sulphide ores include copper pyrites (CuFeS2) and iron pyrites
(FeS2). The sulphate ores include gypsum (CaSO4.2H2O) and anhydrite
(CaSO4). Petroleum gas and coal mines contain sulphur in the form of hydrogen
sulphide gas.

Extraction Of Sulphur
Sulphur deposits in the USA occur at about 200 metres below the earth’s surface.
A strata of loose sand and clay above the sulphur deposits make ordinary mining
impossible. A special method of mining called the Frasch process is therefore
employed. The process is based on the low melting point of sulphur which
ranges between 113 °C and 119°C. In the Frasch process, three concentric pipes
of different diameters 2 cm, 8 cm, and 15 cm are sunk into the sulphur deposits
underground as shown in figure 5.1.

Figure 5.1. The Frasch process

Water is heated to about 170°C under pressure of about 10 atmospheres and

is forced down the outermost pipe. The pressure ensures that the water remains
in liquid state at such high temperature.
Hot air at a pressure of 15 atmospheres is forced down the innermost pipe.
This produces a light froth consisting of a mixture of molten sulphur and water.
The high pressure forces the mixture up the middle pipe. See figure 5.1.
The mixture is run into large tanks on the surface where the sulphur solidifies
at 115°C, Separates from the water and is stored. Sulphur obtained this way in
usually over 99% pure.

Allotropes of Sulphur
Sulphur exhibits allotropy. The main allotropes are rhombic and monoclinic
sulphur.
Experiment 5.1(a): How is rhombic sulphur prepared?
Place two spatulafuls of powdered sulphur in a boiling tube containing 10 cm3 of
carbon(IV) sulphide. Stir and filter the contents of the tube into a dry beaker
using a dry filter paper. Allow the filtrate to evaporate slowly. Use a hand lens to
examine the crystals formed.

Experiment 5.1(b): How is monoclinic sulphur prepared?

Place some powdered sulphur in an evaporating dish and heat gently until the
sulphur melts. Using a glass rod, stir and add more sulphur a little at a time until
the dish is almost full of molten sulphur.
Remove the source of heat and allow the sulphur to cool and form a crust on
the surface. Using a thin glass rod, carefully pierce two holes on widely
separated points in the crust as shown in figure 5.2.

Fig. 5.2: Preparation of monoclinic sulphur.

Immediately pour out the molten sulphur. Remove the crust by cutting round the
edge of the dish with a knife. Use a hand lens to observe the crystals that have
formed on the underside of the crust.

Fig.5.3: Crystals of monoclinic sulphur as seen using a hand lens.

Draw the shapes of rhombic and monoclinic crystals of sulphur.

Discussion
Rhombic sulphur is also referred to as octahedral or α-sulphur. It is a bright
yellow crystalline solid with an octahedral shape as shown in figure 5.4 (a) and
(b).

Fig. 5.4: (a) A crystal of rhombic sulphur

(b) Packing of rhombic sulphur molecules in a crystal

Rhombic sulphur melts at 113°C and has a density of 2.06 g/cm3. It is the stable
allotrope below 96°C. Above this temperature, it slowly changes into monoclinic
sulphur. Monoclinic sulphur is also referred to as prismatic or ß - sulphur. It is a
pale yellow crystalline solid. The crystals appear needle-like when observed
using a hand lens. The actual shape of the crystal is a hexagonal prism. See
figure 5.5 (a) and (b) Monoclinic sulphur has a melting point of 119°C and a
density of 1.98 g/cm3. Below 96°C monoclinic sulphur gradually changes to
rhombic sulphur. This temperature of 96°C is the transition temperature for
rhombic and monoclinic sulphur. The temperature at which one allotrope of an
element changes to another is called the transition temperature.

Fig. 5.5: (a) A crystal of monoclinic sulphur.

(b) Packing of monoclinic Sulphur molecules in a crystal

Sulphur also exists in non-crystalline – (amorphous) forms namely plastic,

colloidal, and powdery sulphur. Plastic sulphur is prepared by heating powdered
sulphur until it boils. The boiling sulphur is then poured in a thin continuous
stream into a beaker containing cold water. Long elastic yellow threads of plastic
sulphur are formed. This form of sulphur is insoluble in carbon(IV) sulphide. It
turns into hard rhombic sulphur if left for a few days. When dilute hydrochloric
acid is added to a test-tube containing a dilute solution of sodium thiosulphate,
Na2S2O3, a yellow precipitate of colloidal sulphur is deposited.
N2S2O3,(aq) + 2HCl(aq) 2NaCl(aq) + H2O(l) + SO2(g) + S(s)
Powdery sulphur may be prepared by saturating distilled water with hydrogen
sulphide. The solution is then exposed to air. A white powder is deposited.
H2S(g) + Water H2S(aq)
2H2S(aq) + O2(g) 2H2O(l) + 2S(s)

Physical Properties of Sulphur

Experiment 5.2 (a): What are the physical properties of sulphur?
Add a small amount of sulphur to a test-tube containing 5 cm3 of water. Shake
the mixture. Record the observation in table 5.1. Repeat the experiment using
benzene, methyl benzene and carbon(IV) sulphide, instead of water.
Table 5.1: Solubility of Sulphur

Solvent Observation

Water

Benzene
 Methylbenzene

Carbon(IV) sulphide

Experiment 5.2(b): What is the effect of heat on sulphur?

Place three spatulafuls of powdered sulphur in a test-tube. Heat the test-tube
gently while occasionally tilting it until the sulphur boils. Note the changes in
colour, and viscosity. Condense the vapour of sulphur on a cold surface.

Answer the following questions

1. In which solvents did sulphur dissolve?
2. What colour changes were observed when sulphur was heated?
3. What changes in viscosity were observed when sulphur was heated?
4. What observations were made when molten sulphur was suddenly cooled?
5. How did the cooled sulphur feel on pressing and stretching?

Discussion
Sulphur is a yellow non-metallic element. A molecule of sulphur consists of a
puckered ring of eight atoms of sulphur joined together by strong covalent bonds
as shown in figure 5.6.

Fig. 5.6: The puckered ring of sulphur molecule

Figure 5.6 shows the puckered ring of a molecule of sulphur. Sulphur is soluble
in organic solvents such as benzene, methyl benzene, and carbon(IV) sulphide. It
does not dissolve in water.
When the yellow powder is gently heated, it melts at 113°C to a clear amber
liquid. At this temperature molten sulphur has a low viscosity, and flows easily.
This liquid is made up of rings of sulphur molecules consisting of eight atoms of
sulphur, S8 as shown in figure 5.6.
On further heating the liquid gradually darkens. At 160°C, it becomes
reddish-brown, and very viscous such that the test-tube may be inverted without
the liquid sulphur pouring out. These changes are due to the breaking of the S8
rings which join to form long chains with over 100,000 atoms of sulphur. As the
chains entangle with one another, the viscosity of the liquid increases.

Fig. 5.7: Long chains of sulphur atoms.

Above 160°C, the liquid darkens further and becomes almost black. Near the
boiling point the liquid becomes more mobile. This is due to the breaking of the
long chains to shorter chains.

Fig. 5.8: Shorter chains of sulphur atoms

The liquid boils at 444°C and forms a reddish-brown vapour consisting of S8, S6
and S2 molecules which cools to form a yellow sublimate. This sublimate is
known as “flowers of sulphur” and consists mainly of S8 rings.

Chemical Properties of Sulphur

Experiment 5.3(a): How does sulphur react with oxygen, iron powder,
copper and concentrated acids?
Carry out the following tests and record your observations as shown in table 5.2.
Table 5.2: Reaction of sulphur with oxygen, iron and copper

Test Observation

1. Place moist litmus paper in a gas jar containing oxygen.

Lower burning sulphur on a deflagrating spoon in a gas jar
as shown in figure 5 9
2. Place a spatulaful of iron powder in a piece of paper. Add an
equal amount of powered sulphur, place the mixture in a
test-tube then heat the mixture strongly. Withdraw the heat
when a red glow is observed. Repeat the experiment using
powdered copper in place of iron.

Fig. 5.9: Burning sulphur in oxygen.

Experiment 5.3 (b): How does sulphur react with concentrated

acids?
Carry out the tests in table 5.3 using samples of sulphur:
Table 5.3: Reaction of sulphur with concentrated acids

Test Observation

1. Add 1 cm3 of concentrated nitric(V) acid to a spatulaful of

sulphur in a test-tube. Heat gently. Add a few drops of
 barium chloride solution to the resulting mixture.
2. Add 1 cm3 of concentrated nitric(V) acid to a spatulaful of
sulphur in a test-tube. Warm gently.
3. Repeat(2) using concentrated hydrochloric acid in place of
concentrated sulphuric acid.

Answer the following questions

1. Write equations for the reactions between sulphur and:
(a) Oxygen.
(b) Iron powder.
(c) Copper powder.
(d) Concentrated nitric(V) acid.
(e) Concentrated sulphuric(VI) acid.
2. Explain any colour changes observed on the litmus paper.
3. Why was barium chloride solution added to the test-tube containing
concentrated nitric(V) acid, and sulphur.

Discussion
Sulphur burns in oxygen with a bright blue flame forming misty fumes with a
choking smell. The gas is mainly sulphur(VI) oxide (sulphur dioxide) SO2, with
traces of sulphur(IV) oxide (sulphur trioxide, SO3).
S(s) + O2(g) SO2(g)
2S(s) + 3O2(g) 2SO3(g)
The moist blue litmus paper turns red indicating that the oxides produced when
sulphur burns are acidic. Sulphur combines directly with some elements to form
sulphides. When a mixture of sulphur, and iron powder is heated, a highly
exothermic reaction occurs. Once the reaction has started at one point, the glow
spreads through the mixture without further heating, forming iron(II) sulphide.
This is because the heat produced during the reaction is high enough to sustain
the reaction.
Hot powdered copper similarly combines with heated sulphur forming copper(I)
sulphide.

Sulphur also combines with some non-metals such as carbon and hydrogen
forming non-metallic sulphides. Carbon combines with sulphur at high
temperatures to form carbon(IV) sulphide. Hydrogen combines with sulphur to
form hydrogen sulphide.

Sulphur is easily oxidised by both concentrated nitric(V) and sulphuric(VI)

acids. When warmed with concentrated nitric(V) acid, sulphur is oxidised to
sulphuric(VI) acid. The sulphate ( ) ion in the acid forms a white precipitate
with barium ions in the solution. The nitric(V) acid itself is reduced to red brown
nitrogen(IV) oxide and water.
S(s) + 6HNO3(aq) H2SO4(aq) + 6NO2(g) + 2H2O(l)
Concentrated sulphuric(VI) acid oxidises sulphur to sulphur(IV) oxide while the
acid is reduced to sulphur(IV) oxide, and water.
S(s) + 2H2SO,(l) 3SO2(g) + 2H2O(l)
Concentrated hydrochloric acid does not react with sulphur because it is not an
oxidising agent.

Uses of Sulphur
• Manufacture of sulphuric(VI) acid.
• As a fungicide.
• In the manufacture of bleaching agent used to bleach wood pulp in the paper
 industry.
• Vulcanisation (hardening) of rubber.
• Used in smaller quantities in the manufacture of dyes, and fireworks.

Rolls of paper at a production facility.

Exercise 5.1
1. In the extraction of sulphur by the Frasch Process, water (at a temperature of
170°C) is pumped into the sulphur deposits.
(a) State the role of the water.
(b) Explain how a temperature of 170°C is achieved.
2. Which allotrope of sulphur:
(i) Is stable at room temperature?
(ii) Has prismatic crystals?
(iii) Has higher density?
3. A small amount of sulphur was burnt in a deflagrating spoon. The burning
sulphur was then lowered into a gas jar full of oxygen.
(a) Write an equation for the reaction that occurs.
(b) The product formed is dissolved in water. State the effect of the
resulting solution on blue and red litmus paper.
4. Study the following flow chart. Use it to answer the questions that follow.
 (a) Identify:
(i) Solid A.
(ii) Solid B.
(ii) Gas E.
(b) Name the reagents used in step:
(i) I
(ii) II
(c) State the conditions X under which sulphur and water were formed.
5. Study the flow chart below and answer the questions that follow.

(a) Name:
(i) Solid A
(ii) Gas B
(b) Write the formula of the anion in the white precipitate C.
 (c) Dilute nitric acid is added to the white precipitate(C). Write the
equation for the reaction.
The Compounds of Sulphur
Oxides of Sulphur
Sulphur forms two oxides namely sulphur(IV) oxide, SO2, and sulphur(VI)
oxide SO3.
Sulphur(IV) Oxide, SO2

Experiment 5.4: How is sulphur(IV) oxide prepared?

Put a spatulaful of sodium sulphate in a round-bottomed flask. Arrange the
apparatus as shown in figure 5.10.

Fig. 5.10: Preparation of sulphur(IV) oxide (sulphur dioxide)

Add dilute hydrochloric acid drop-wise and warm. Collect the gas in six test-
tubes and preserve for experiment 5.5.

Answer the following questions

1. Write an equation for the reaction that occurs between dilute sulphuric(VI)
acid and sodium sulphite.
2. What is the purpose of the concentrated sulphuric(VI) acid in the
experiment?
3. What is the purpose of the paper soaked in potassium dichromate(VI).
Discussion
Sulphur(IV) oxide is prepared in the laboratory by the action of dilute
hydrochloric acid on a suitable sulphite such as sodium sulphite.
Na2SO3(s) + 2HCl(aq) SO2(g) + 2NaCl(aq) + H2O(l)
The gas may also be prepared by the action of concentrated sulphuric(VI) acid
on copper turnings. The reaction should be carried out in a fume cupboard.
Cu(s) + 2H2SO4(aq) SO2(g) + 2H2O(l) + CuSO4(aq)
Sulphur(IV) oxide is dried by passing it through concentrated sulphuric(IV) acid
and collected by downward delivery. The gas jar is confirmed to be full of the
gas when the paper soaked in orange potassium chromate(VI) turns green.

Physical Properties of Sulphur(IV) Oxide

Experiment 5.5: What are the physical properties of sulphur(IV)

oxide?
Carry out the following tests on sulphur(IV) oxide gas and record your
observations as shown in table 5.4.
Table 5.4: Some properties of sulphur(IV) oxide.

Test Observation

1. Note the colour of the gas.

2. Note the smell of the gas. (Caution: Do not smell directly).

3. Invert a test-tube full of sulphur(IV) oxide in a trough of

water.
4. Drop a dry and a damp piece of blue litmus paper into a test-
tube containing sulphur(IV) oxide.
5. Put a few drops of universal indicator into a test-tube
containing about 5 cm3 of water. Using a dropper transfer a
few drops of the solution into a test-tube containing the gas.
Shake the mixture.
 6. Put a few drops of universal indicator in a test-tube
containing 5 cm3 of 0.1 M sodium hydroxide solution.
Transfer a few drops of the solution into a test-tube
containing sulphur(IV) oxide and shake the mixture.

Answer the following questions

1. Give a reason why sulphur(IV) oxide is collected as shown in figure 5.11.
2. Explain the observation made when a test-tube full of sulphur(IV) oxide is
inverted in a trough of water.
3. Explain the observation made when:
(a) A damp litmus paper was dropped into a test-tube containing
sulphur(IV) oxide gas.
(b) Sodium hydroxide solution is added to sulphur(IV) oxide.
4. Write an equation for the reaction between sulphur(IV) oxide and:
(a) Water.
(b) Dilute sodium hydroxide.

Discussion
Sulphur(IV) oxide is a colourless poisonous gas with a characteristic irritating,
and choking smell. It has a boiling point of –10°C and is readily liquefied under
pressure. It is denser than air, hence can be collected by downward delivery.
When a test-tube full of the gas is inverted in a trough of water, the water level
rises rapidly inside the test-tube. This shows that the gas is soluble in water.
When a moist blue litmus paper is dropped into a test-tube containing
sulphur(IV) oxide, it turns red showing that the gas is acidic. The gas has no
effect on dry litmus. The solution of the gas in water is sulphuric(IV) acid. This
is a weak dibasic acid.
SO2(g) + H2O(l) H2SO3(aq)
The acid is responsible for the change in colour of the moist litmus. When
sodium hydroxide solution is added to sulphur(IV) oxide gas, neutralisation
occurs. The sulphuric(IV) acid formed reacts with sodium hydroxide forming a
salt and water. During the reaction between the acid and sodium hydroxide, two
types of salts are formed, a normal and an acid salt.
Bleaching Action of Sulphur(IV) Oxide

Experiment 5.6: How does sulphur(IV) oxide bleach?

Carry out the following test and record the observation as in table 5.5.
Table 5.6: Bleaching action of sulphur(IV) oxide

Test Observation

Place blue or red flower petals in a gas jar containing

sulphur(IV) oxide.

Answer the following question

Explain the observation made in the gas jar in table 5.6.

Discussion
When coloured flowers are dropped into a gas jar containing sulphur(VI) oxide,
the flowers are bleached. Sulphur(IV) oxide combines first with the moisture,
forming sulphuric(IV) acid. The sulphuric(IV) acid then combines with oxygen
from the dye to form sulphuric(VI) acid. When the dye loses oxygen it becomes
colourless. In this reaction, the dye undergoes reduction while the sulphuric(IV)
acid is oxidised.
SO2(g) + H2O(l) H2SO3(aq)
H2SO3(aq) + Dye H2SO4(aq) + Colourless material.
During the manufacture of paper, reducing agents such as sulphuric(IV) acid are
used to bleach the materials. When such paper is exposed to the atmosphere in
the presence of sunlight, the oxygen removed during bleaching is restored. This
explains why newsprint paper turns brown after sometime.
Reducing Action of Sulphur(IV) Oxide
Experiment 5.7: What are the reducing properties of sulphur(IV)
oxide?
Carry out the following tests on sulphur(IV) oxide gas and record the
observations as in table 5.7.
Table 5.7: Reducing properties of sulphur(IV) Oxide

Test Observation

1. Add 2 cm3 of dilute sulphuric(VI) acid to an equal volume of

potassium dichromate(VI) in a test-tube. Transfer a portion
of the solution into a test-tube containing sulphur(IV) oxide
gas. Shake the mixture.
2. Add 2 cm3 of dilute sulphuric(VI) acid to an equal volume of
potassium dichromate(VI) in a test-tube. Transfer a portion
of the solution to a test tube containing SO2 gas and shake
the mixture.
3. Add 2 cm3 of dilute hydrochloric acid to 2 cm3 of bromine
water in a test-tube. Transfer some portion of the solution to
a test-tube containing SO2 and shake.

4. To a test-tube full of sulphur(IV) oxide gas add 1 cm3 of

concentrated nitric(V) acid. Shake the test-tube then add a
few drops of barium chloride solution.
5. Warm 3 cm3 of iron(III) chloride solution and transfer a
portion of the solution to a test-tube containing SO2 gas.

6. Lower a burning splint into a gas jar of SO2.

Answer the following questions

1. Explain the observations made when sulphur(IV) oxide gas is reacted with:
(i) Acidified potassium chromate(VI) solution.
(ii) Acidified potassium manganate(VII) solution.
(iii) Acidified bromine water followed by a few drops of barium chloride
 solution.
2. Write equations for the reactions in (i) above.
3. Explain the observations made when:
(i) Concentrated nitric(V) acid is added to a test-tube full of sulphur(IV)
oxide, followed by barium chloride solution.
(ii) Sulphur(IV) oxide is reacted with a hot solution of iron(II) chloride.
4. Write equations for the reactions in (3).

Discussion
Sulphur(IV) oxide is a strong reducing agent. The reducing property is only
displayed when the gas is in aqueous state. Acidified potassium dichromate(VI)
turns from orange to green when reacted with sulphur(IV) oxide. The
chromium(VI) ion in the dichromate ( ) is reduced to chromium(III) ion.

This is a test for sulphur(IV) oxide. The colour of acidified potassium

manganate(VII) turns from purple to colourless when reacted with sulphur(IV)
oxide. This is because the manganese(VII) ion in the manganate ion ( ) is
reduced to manganese(II) ion.

Red brown acidified bromine water is decolourised when reacted with

sulphur(IV) oxide. The bromine water is reduced to hydrobromic acid as the
sulphur(IV) oxide is oxidised to sulphate.

When a solution of barium chloride is added to the mixture, a white precipitate

of barium sulphate is formed indicating the presence of sulphate, ions.
When concentrated nitric(V) acid is added to a test-tube containing sulphur(IV)
oxide gas brown fumes of nitrogen(IV) oxide are given off.

The nitric(V) acid is reduced to nitrogen(IV) oxide while the sulphuric(IV) acid
is oxidised to sulphuric(VI) acid. When warm iron(III) chloride solution is added
to sulphur(IV) oxide the yellow colour changes to green. Sulphur(IV) oxide
reduces yellow iron(III) ions, Fe3+(aq) to pale green iron(II), Fe2+(aq) ions.

Similarly, hydrogen peroxide is reduced to water.

When a burning splint is lowered into a test-tube containing sulphur(IV) oxide, it

is put off showing that the gas does not support combustion or burn. However, in
the presence of a catalyst, the gas is oxidised to sulphur(VI) oxide.

Oxidising Action of Sulphur(IV) Oxide

Experiment 5.8: What is the oxidising action of sulphur(IV) oxide?
Carry out the following test and record the observation as in table 5.8.
Table 5.8: Oxidising action of sulphur(IV) oxide

Test Observation

1. Lower a burning piece of magnesium on a deflagrating

spoon into a gas jar of sulphur(IV) oxide.

Answer the following questions

1. Explain the observations made when:
(a) Burning magnesium is lowered into a gas jar of sulphur(IV) oxide.
(b) Write an equation for the reaction that takes place in (a).

Discussion
When burning magnesium is lowered into a gas jar of sulphur(IV) oxide, it
continues to burn for some time. White fumes of magnesium oxide, and yellow
specks of sulphur are formed.
Burning magnesium continues to burn in sulphur(IV) oxide because the heat
produced by the burning magnesium decomposes the sulphur(IV) oxide to
sulphur and oxygen. The magnesium combines with the oxygen to form
magnesium oxide.

In this reaction, sulphur(IV) oxide is an oxidising agent, supplying oxygen to

magnesium.
When a gas jar of dry hydrogen sulphide gas is inverted over a test-tube
containing dry sulphur(IV) oxide, there is no observable change. When a few
drops of water are added into each gas jar and the mixture is shaken, a yellow
deposit of sulphur is produced.
2H2S(g) + SO2(g) 3S(s) + 2H2O(l)
The reaction only takes place when the gases are moist. Sulphur(IV) oxide acts
as an oxidising agent.

Preparation of Sulphur(IV) Oxide (SO3)

In the laboratory, sulphur(VI) oxide is prepared by reacting sulphur(IV) oxide
with oxygen in the presence of a platinum catalyst. Figure 5.1 shows a set up of
the apparatus.
Fig. 5.11: Lab Preparation of Sulphur Trioxide, SO3

Equation for the reaction taking place,

2SO2(g)+ O2(g) 2SO3(s)

Other Methods
Decomposing of sodium hydrogen sulphate.

Answer the following questions

1. State the purpose of the following in the set up.
(a) Concentrated sulphuric(VI) acid.
(b) Freezing salt ice mixture.
(c) Anhydrous calcium chloride.
2. Write an equation for the reaction that takes place in the combustion tube.
3. Comment on the method of collection of sulphur(VI) oxide.

During the preparation of sulphur(VI) oxide, sulphur(IV) oxide and oxygen

gases are dried by passing them through concentrated sulphuric(VI) acid. The
dried gases are then mixed and passed over heated platinum catalyst. The
following reaction takes place.
2SO2(g)+ O2(g) 2SO3(s)
The sulphur(VI) oxide is cooled by the freezing salt-ice mixture and it solidifes.
This allows it to be collected as illustrated. Since sulphur(VI) oxide is
deliquescent, calcium chloride is used to keep it free from moisture.

Test for Sulphate and Sulphite ions

Experiment 5.8: What is the test for sulphate and sulphate and
sulphite ions?
Prepare solutions containing sulphate, and sulphite ions respectively. Carry out
the following tests and record the observations as in table 5.9.
Table 5.9: Test for sulphate and sulphite ions
 Test Observation

To 2 cm3 of sodium sulphate in a test-tube:

(i) Add 2 cm3 of barium chloride(or nitrate) solution.

(ii) To the mixture in(i) above add 2 cm3 of dilute hydrochloric

acid (or dilute nitric(V) acid).
Repeat procedure (i) and (ii) using 2 cm3 solution of sodium
sulphite.

Answer the following questions

1. State the observations made when barium chloride solution is added to:
(a) Sodium sulphate solution.
(b) Sodium sulphite solution.
2. Why is the acid added to the mixture?
3. Write ionic the equation where possible for the reaction in (i) and (ii).

Discussion
When barium chloride solution is added to sodium sulphate and sodium sulphite
solutions, a white precipitate is formed in each case. The white precipitates are
barium sulphate and barium sulphite respectively.

When dilute hydrochloric acid is added to the mixture containing barium

sulphate precipitate, the precipitate does not dissolve. However, when dilute
hydrochloric acid is added to the mixture containing barium sulphite precipitate,
the precipitate dissolves. This is the test for sulphite ions.

BaSO3(s) + 2HCl(aq) BaCl2(aq) + SO2(g) + H2O(l)

BaSO3(s) + 2H+(aq) Ba2+(aq) + SO2(g) + H2O(l)
Uses of Sulphur(IV) Oxide
Sulphur(IV) oxide is used:
• As a major raw material in the large scale manufacture of sulphuric(VI) acid.
• To make calcium hydrogen sulphite, Ca(HSO3)2, used to bleach wood pulp in
the manufacture of paper.
• As a fumigant.
• As a preservative in jam and fruit juices.

Exercise 5.2
1. Explain why moist blue litmus paper is bleached when it is put in a gas jar
containing sulphur(IV) oxide while dry litmus is not bleached.
2. A piece of old newspaper which had turned brown was moistened and
placed in a gas jar containing sulphur(IV) oxide. State and explain the
observations made.
3. Solid M is suspected to contain the sulphate ions. Describe the steps you
would follow to show the presence of sulphate ions in the solid.
4. Presence of nitrogen and sulphur oxides in the atmosphere cause
environmental pollution. Nitrogen(IV) oxide reacts with sulphur(IV) oxide
according to the equation,
SO2(g) + NO2(g) SO3(g) + NO(g)
(a) Identify the reducing agent in the above reaction. Explain your choice.
(b) State two effects of acid rain.
(c) Explain the term scrubbing of sulphur(IV) oxide.

Large Scale Manufacture of Sulphuric(VI) Acid

Sulphuric(IV) acid is manufactured by the contact process. The raw materials
for its manufacture are sulphur(IV) oxide and air. The flow diagram in figure
5.12 summarises the contact process.
Fig. 5.12 Large scale manufacture of sulphuric acid

Sulphides or sulphur are burnt in air to produce sulphur(IV) oxide. Burning of

sulphur is the most convenient method of producing sulphur(IV) oxide.
S(s) + O2(g) SO2(g)
The sulphur(IV) oxide contains dust particles as impurities. The impurities
reduce the surface area of the catalyst, thus impairing its efficiency. These
impurities are said to poison the catalyst. The dust impurities are removed by
electrostatic precipitation. The mixture of gases is passed through concentrated
sulphuric(IV) acid in order to dry it. After purification, the gaseous mixture is
pre-heated in the heat exchanger to attain suitable reaction temperature before
being passed into the catalytic chamber. In the catalytic chamber, sulphur(IV)
oxide and oxygen react to form sulphur(VI) oxide.

Either platinum or vanadium(V) oxide may be used as catalyst. However, the

vanadium(V) oxide(V2O5) is preferred because it is cheaper and less easily
poisoned. For maximum yield of sulphur(VI) oxide in the contact process, low
temperature and high pressure are necessary. However, at low temperature the
reaction is slow while high pressure is expensive to maintain. A compromise
temperature of 450°C and pressure of 2 to 3 atmospheres are used. The
temperature of 450°C and pressure of 2 to 3 atmospheres are referred to as
optimum conditions.
The sulphur(VI) oxide is not dissolved directly in water because the
excessive heat generated could boil the acid to produce a mist of fine droplets of
sulphuric(VI) acid in air. Hence, the gas is dissolved in concentrated
sulphuric(VI) acid to form oleum (H2S2O7).

Sulphuric(VI) acid is obtained by diluting oleum with water.

H2S2O7(1) + H2O(l) 2H2SO4(l)
In Kenya, sulphuric(VI) acid is manufactured in Thika by Kel Chemicals
Ltd. During the contact process, not all the sulphur(IV) oxide is converted into
sulphur (VI) oxide: only 98% conversion of sulphur(IV) oxide to sulphur(VI)
oxide occurs. Sulphur(IV) oxide is a pollutant. Therefore, passing the exhaust
gases through chimneys lined with calcium hydroxide reduces the amount of
sulphur(IV) oxide released to the atmosphere. This is referred to as scrubbing the
gas.
Ca(OH)2(aq) + SO2(g) CaSO3(s) + H2O(l)
In some industries, filters fitted with strong alkalis are installed to remove any
traces of acid or mist from exhaust gases.

A section of the sulphuric acid manufacturing plant, Thika.,

Properties of Sulphuric(VI) acid

Experiment 5.11: What are the properties of concentrated

sulphuric(VI) acid?
Carry out the following tests on concentrated sulphuric(VI) acid and record the
results in table 5.10.
Table 5.10: Properties of concentrated sulphuric (VI) acid

Test Observation

1. (a) Add 2 cm3 of concentrated sulphuric(VI) acid to a

spatulaful of copper(II) sulphate crystals in a test-tube.
(b) Add 5 cm3 of concentrated sulphuric(VI) acid to one
spatulaful of sucrose crystals in a 100 cm3 beaker.
(c) Add 2 cm3 of concentrated sulphuric(VI) acid to 2 cm3 of
ethanol and heat. Bubble the gas produced through
potassium manganate(VII) solution.
2. (a) Add 2 to 3 pieces of copper foil to 2 cm3 of concentrated
sulphuric(VI) acid in a boiling tube and warm gently. Test
the gas produced with a paper soaked in acidified
potassium chromate(VI).
(b) Add a spatulaful of zinc granules to 2 cm3 of concentrated
sulphuric(VI) acid, and warm gently. Test the gas evolved
with a paper soaked in acidified potassium chromate(VI)
paper.
(c) Add a spatulaful of powdered charcoal (carbon) to 2 cm3
of concentrated sulphuric(VI) acid and warm gently. Test
the gas evolved with lime water.
3. (a) Carefully add 2 cm3 of concentrated sulphuric(VI) acid to
one spatulaful of potassium nitrate crystals in a test-tube.
Warm the mixture gently and test the gas produced with
moist blue litmus paper.
(b) Repeat experiment 3(a) using sodium chloride crystals
instead of potassium nitrate crystals. Test the gas produced
with
(i) Moist blue litmus paper.
(ii) Concentrated ammonia.

Answer the following questions

 1. Explain why the acid should be added to water and not water to acid.
2. Explain the observation made when concentrated sulphuric(VI) acid was
added to:
(a) Copper(II) sulphate crystals.
(b) Sugar crystals.
(c) Ethanol.
3. Write equations for these reactions.
4. Explain the observations made when concentrated sulphuric(IV) acid was
reacted with:
(a) Copper metal.
(b) Carbon.
(c) Zinc metal.
(d) Sulphur powder.
5. Explain the observation made when concentrated sulphuric(VI) acid was
added to:
(a) Potassium nitrate crystals.
(b) Sodium chloride.
Write the equations for the reactions that occurred.

Discussion
Concentrated sulphuric(VI) acid is a colourless oily liquid. It has a density of
1.84 g/cm3 and boils at 338°C. It is very soluble in water. If water is added to the
acid, fumes are produced since the reaction is quite exothermic. For this reason,
dilution of the concentrated acid should always be carried out by adding small
portions of the acid slowly to a large volume of water with constant stirring.
Concentrated sulphuric(VI) acid is hygroscopic. This property makes the acid a
suitable drying agent for gases which do not react with it. The acid readily
removes water from hydrated salts. When the acid is added to blue crystals of
copper(II) sulphate pentahydrate, CuSO4.5H2O, a white powder of the
anhydrous salt is formed.

Note:
Never add water into the concentrated
acid.
Concentrated sulphuric(VI) acid is also capable of removing elements of water
(hydrogen and oxygen) from compounds which do not contain water molecules.
When concentrated sulphuric(VI) acid is added to sugar crystals, the crystals are
charred to a black mass.

The process of removing water or its elements from a compound is called

dehydration. A dehydrating agent is a substance which is capable of removing
chemically combined water or the elements of water from a compound.
Concentrated sulphuric(VI) acid is a strong dehydrating agent. Methanoic acid is
dehydrated to form carbon(II) oxide.

The acid also dehydrates alcohols to alkenes.

Hot concentrated sulphuric(VI) acid is a strong oxidising agent. When copper or

zinc metal is added to concentrated sulphuric(IV) acid, a gas is produced which
turns acidified potassium chromate(VI) solution from orange to green and
decolourises acidified potassium manganate(VII) solution.
Cu(s) + 2H2SO4(l) CuSO4(aq) + SO2(g) + 2H2O(l)
Zn(s) + 2H2SO4(l) ZnSO4(aq) + SO2(g) + 2H2O(l)
Hot concentrated sulphuric(VI) acid also oxidises non-metals such as sulphur
and carbon.
S(s) + 2H4SO4(l) 3SO2(g) + 2H2O(l)
 C(s) + 2H2SO4(l) 2SO2(g) + CO2 (g) + 2H2O(l)
Concentrated sulphuric(IV) acid is a less volatile acid. It displaces more volatile
acids from their salts.
KNO3(s) + H2SO4(l) HNO3(g) + KHSO4(s)
NaCl(s) + H2SO4(l) HCl(s) + NaHSO4(s)

Reactions of Dilute Sulphuric(VI) Acid

Experiment 5.12: How does dilute sulphuric(VI) acid react with

metals?
Place a 2 cm piece of clean magnesium ribbon in a test-tube. Add about 4 cm3 of
dilute sulphuric(VI) acid. Test the gas produced using a burning splint. Repeat
the experiment using a zinc granule and a few pieces of copper turnings in place
of magnesium. Record your observations as in table 5.11.
Table 5.11 Reactions of dilute H2SO4 with metals

Metal Observation

1. Magnesium

2. Zinc

3. Copper

Answer the following questions

1. State the observation made when dilute sulphuric(VI) acid is added to:
(a) Magnesium.
(b) Zinc.
(c) Copper.
2. Write equations for the reactions between dilute sulphuric(VI) acid and:
(a) Magnesium.
(b) Zinc.
 3. Explain why no gas is produced when dilute sulphuric(VI) acid is added to
copper turnings.

Discussion
When dilute sulphuric(VI) acid is added to magnesium or zinc, an effervescence
occurs as a colourless gas which produces a ‘pop’ sound when a burning splint is
applied is produced. The reaction between magnesium and dilute sulphuric acid
is more vigorous than that of zinc and dilute sulphuric(VI) acid.
Mg(s) + H2SO4 (aq) MgSO4(aq) + H2(g)
Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
Copper is below hydrogen in the reactivity series of the metals. It does not
therefore displace hydrogen from dilute sulphuric(VI) acid. The reactions
between metals high in the reactivity series such as potassium and sodium with
dilute acids are very violent and should never be attempted. The vigour of the
reaction decreases as you go down the reactivity series.

Experiment 5.12: How does dilute sulphuric(VI) acid react with

carbonates
Add a spatulaful of sodium carbonate into a clean dry test-tube. Add 4 cm3 of
dilute sulphuric(VI) acid. Test the gas that is produced using lime water. Repeat
the experiment using zinc carbonate, calcium carbonate, and copper(II)
carbonate in place of sodium carbonate. Record your observations in table 5.12.
Table 5.12: Reaction of dilute of dilute sulphuric(VI) acid with carbonates

Test Observation

1. Sodium carbonate

2. Zinc carbonate

3. Calcium carbonate

4. Copper(II) carbonate
 Answer the following questions
1. State the observation made when dilute sulphuric(VI) acid is added to
carbonates.

Discussion.
Effervescence occurs when dilute sulphuric(VI) acid is added to the carbonates
of zinc, sodium and copper. The colourless gas produced forms a white
precipitate with lime water showing that it is carbon(IV) oxide.
ZnCO3(s) + H2SO4(aq) ZnSO4(aq) + H2O(l) + CO2(g)
Na2CO3(s) + H2SO4(aq) Na2SO4(aq) + H2O(l) + CO2(g)
CuCO3(s) + H2SO4(aq) CuSO4(aq) + H2O(l) + CO2(s)
The reaction between calcium carbonate and dilute sulphuric(VI) acid stops soon
after it starts. This is because the calcium sulphate produced during the reaction
is insoluble.
CaCO3(s) + H2SO4(aq) CaSO4(s) + H2O(l) + CO2(g)
The insoluble calcium sulphate forms a coating on the sulphate calcium
preventing further contact with the acid. As a result the reaction stops. Lead(II)
carbonate behaves in a similar manner.

Experiment 5.13: How does dilute sulphuric(VI) acid react with

metal oxides and hydroxides?
Place a spatulaful of each of the metal oxides listed in table 5.13 in clean dry
test-tube. Add 5 cm3 of 2 M sulphuric(VI) acid. Warm if necessary. Repeat the
experiment using 5 cm3 of 2 M sodium hydroxide solution. Record your
observations in table 5.13.
Table 5.13. Reactions of dilute sulphuric(VI) acid with metal oxides and hydroxides

Metal oxide or hydroxide Observation

Magnesium oxide

Zinc oxide
 Copper(II) oxide

Lead(II) oxide

Sodium hydroxide

Answer the following questions

1. Write equations for the reactions in experiment 5.14.
2. Which metal oxide reacted differently? Explain.

Discussion
When dilute sulphuric(VI) acid reacts with a metal oxide or hydroxide, a salt and
water are formed. However, those metal oxides whose sulphates are insoluble
react only for a short while. Thus, the reaction between dilute sulphuric(VI) acid,
and lead(II) oxide stops almost immediately. This is due to the formation of an
insoluble layer of lead(II) sulphate which effectively prevents further contact
between the acid and the oxide.

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

Uses of Sulphuric(VI) acid

1. Manufacture of fertilisers.
2. Processing of metal ores.
3. Manufacture of detergents.
4. Manufacture of plastics.
5. Manufacture of dyes and paints.
6. Used in lead acid accumulators.

Hydrogen Sulphide (H2S)

Hydrogen sulphide is a gaseous compound of sulphur which is very poisonous.
It occurs naturally in some deposits mixed with natural gas. The set-up in figure
5.13 can be used to prepare hydrogen sulphide.

Figure 5.13 Preparation hydrogen sulphide.

Hydrogen sulphide is formed when dilute hydrochloric acid is added to iron(II)

sulphide.
FeS(s) + 2HCl(aq) FeCl2(aq) + H2S(g)
However, any metal sulphide, and dilute acid can be used to prepare hydrogen
sulphide gas. The gas is collected over warm water since it dissolves in cold
water. The gas can be dried by passing it through a U-tube packed with
anyhydrous calcium chloride. The gas cannot be dried using concentrated
sulphuric(VI) acid because it would be oxidised to sulphur.
3H2S(g) + H2SO4(l) 4S(s) + 4H2O(l)

Physical properties of hydrogen sulphide

Hydrogen sulphide is a colourless gas with a characteristic smell of rotten eggs.
It is very poisonous. It is slightly soluble in cold water. It is denser than air.

Chemical properties of hydrogen sulphide

(a) Reaction with water
Hydrogen sulphide dissolves in water to form a weak acidic solution of H2S(aq).

Aqueous hydrogen sulphide is a weak dibasic acid. It forms two types of salts,
the hydrogen sulphides, and the sulphides, e.g., sodium hydrogen sulphide
(NaHS) and sodium sulphide (Na2S).

(b) Reaction with Oxygen

Hydrogen sulphide burns in air with a pale blue flame. In a limited supply of air,
sulphur and water are formed.
2H2S(g) + O2(g) 2S(s) + 2H2O(g)
In excess air, sulphur(IV) oxide and water are formed.
2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(g)

(c) Reactions of hydrogen sulphide as a reducing agent

Hydrogen sulphide is a strong reducing agent and is readily oxidised to sulphur,
which is precipitated as a yellow solid. Red-brown bromine water is reduced by
hydrogen sulphide forming colourless hydrogen bromide solution and a yellow
precipitate of sulphur.
Br2(aq) + H2S(g) 2HBr(aq) + S(s)
Yellow iron(III) chloride in solution is reduced to green iron(II) chloride.
H2S(g) + 2FeCl3(aq) 2FeCl2(aq) + S(s) + 2HCl(aq)
Acidified purple potassium manganate(VII) solution is reduced to a colourless
manganese(II) solution.

Similarly, acidified orange chromate(VI) is reduced to green chromium(III) ions

solution.
A solution of hydrogen peroxide is reduced to water, and a yellow precipitate of
sulphur is formed.
H2O2(aq) + H2S(g) 2H2O(l) + S(s)
Brown fumes of nitrogen(IV) oxide are produced and pale yellow sulphur is
deposited when hydrogen sulphide is bubbled into dilute nitric(V) acid.
2HNO3(aq) + H2S(g) 2NO2(g) + 2H2O(l) + S(s)
Dilute sulpharic(VI) acid is reduced to sulphur by hydrogen sulphide.
H2SO4(aq) + 3H2S(g) 4S(s) + 4H2O(T)

(d) Reaction with aqueous metallic ious

Hydrogen sulphide reacts with some metal ions in solution to form precipitates
of metal sulphides. When bubbled through aqueous copper(II) sulphate, a black
precipitate of copper(II) sulphide is formed.
Cu2+(aq) + S2-(aq) CuS(s)
Other metal sulphides are precipitated as shown by the following ionic
equations.
Zn2+(aq) + S2-(aq) ZnS(s)
Pb2+(aq) + S2-(aq) PbS(s)
Fe2+(aq) + S2-(aq) FeS(s)
Most sulphides are insoluble in water except those of sodium, potassium and
ammonium. When equal volumes of equimolar hydrogen sulphide and sodium
hydroxide solutions are reacted, sodium hydrogen sulphide, an acid salt is
formed.
NaOH(aq) + H2S(aq) NaHS(aq) + H2O(l)
When excess sodium hydroxide is used sodium sulphide, a normal salt is
formed.
2NaOH(aq) + H2S(aq) Na2S(aq) + 2H2O(l)

Exercise 5.3
1. Study the flow chart below and answer the questions that follow.
 (a) Identify A, B, C and D, and write equations for the reactions which
occurred.
(b) Suggest a suitable drying agent for gas A.
(c) State and explain what would happen to the yield of product C if the
temperature of the catalyst were raised to 600°C.
(e) Write an ionic equation for the reaction which would occur between
solution D and zinc metal.
2. Write the observations and the equations of the reactions which occur when
concentrated sulphuric(VI) acid reacts with each of the following:
(a) Potassium nitrate.
(b) Copper(II) sulphate crystals.
(c) Sugar.
(d) Copper metal.
3. (a) Name two catalysts that could be used in the contact process. Give
reasons why one of the catalysts is prefered to the other.
(b) What is meant by the following terms in relation to the manufacture of
sulphuric(VI) acid?:
(i) "Poisoning a catalyst."
(ii) "Optimum conditions"
Pollution of the Atmosphere by Compounds of Sulphur
Sulphur compounds especially sulphur(IV) oxide and hydrogen sulphide, are
among the major atmospheric pollutants. Sulphur(IV) oxide is usually emitted
into the atmosphere when sulphur containing fuels are burnt. Some sulphur(IV)
oxide is also emitted during the extraction of metals such as copper and in the
manufacture of sulphuric(VI) acid. In the atmosphere sulphur(IV) oxide
dissolves in water to form sulphuric(IV) acid.
 SO2(g) + H2O(l) H2SO3(aq)
The sulphuric(IV) acid is then oxidised by atmospheric oxygen to sulphuric(VI)
acid, which comes down as acid rain or acid fog. These have serious
environmental effects. These include:

• Stunted growth in plants due to loss of chlorophyll from plants' leaves.

• Death of plants as a result of defoliation.
• Destruction of aquatic life in acidified lakes.
• Corrosion of stone work on buildings.
• Corrosion of metallic structures.
• Leaching of minerals in the soil.
• Irritation of the respiratory system.

Summary
1. Sulphur exists naturally in deposits as an element. It also occurs in
combined form as sulphides and sulphates.
2. The element exists in two main allotropic forms – rhombic and monoclinic.
3. Sulphur forms two oxides namely sulphur(IV) oxide and sulphur(VI) oxide.
4. Sulphur(IV) oxide can be prepared in the laboratory by the action of dilute
acid on a sulphite, or concentrated sulphuric(VI) acid on copper metal or
sulphur.
5. Sulphur(IV) oxide reacts with water to form sulphuric(IV) acid, H2SO3,
which is a strong reducing agent.
6. Sulphur(IV) oxide acts as an oxidising agent when reacted with stronger
reducing agents such as hydrogen sulphide.
7. Concentrated sulphuric(VI) acid is hygroscopic and is used as a dehydrating
agent.
8. Dilute sulphuric(VI) acid shows characteristic acid properties when reacted
with metals, metal oxides, hydroxides and carbonates.
9. Concentrated sulphuric(VI) acid is a strong oxidising agent. It oxidises
metals such as copper and non-metals such as sulphur and carbon and is
itself reduced to sulphur(IV) oxide.
10. Concentrated sulphuric(VI) acid displaces more volatile acids such as
hydrogen chloride and nitric acid from their salts.
Revision Exercise
1. Sulphur has two allotropes, rhombic and monoclinic. The transitional
temperature of these allotropes is 96°C. Use the following flow chart to
answer the questions that follow.
(a) Identify:
(i) Allotrope A.
(ii) Allotrope B.
(iii) Brown gas C.
(iv) Solution D.

(b) Write a balanced equation for the reaction between allotrope A and hot
concentrated nitric(V) acid.
(c) Allotrope A is mixed with Iron filings and heated.
(i) State the observation made.
(ii) Name the product formed.
(iii) Write a balanced equation for the reaction.
2. Study the flow chart below and answer the questions that follow.
(a) Name the white precipitate.
(b) Write the formula of the potassium salt.
(c) Name gas Q.
 (d) Write a balanced equation for the reaction between aqueous
hydrochloric acid and solid X.
3. Study the flow chart below and answer the questions that follow.
(a) Identify J, K, L, M and N.
(b) (i) Write an equation for the reaction that occurs between solid M and
dilute sulphuric acid.
(ii) Write an ionic equation for the reaction between N and copper(II)
sulphate solution.
(c) State and explain the observations made when N is bubbled through:
(i) Iron(III) chloride solution.
(ii) Dilute nitric acid.
4. Study the flow chart below and answer questions (a) to (i).

(a) State the reagent required in step I.

(b) Name gas A.
 (c)State the observation made when step II takes place.
(d) State the conditions required for step(III) to occur.
(e)Write a balanced equation for the reaction in(d) above.
(f)Explain how step IV occurs in the Contact process.
(g) Name the chemical used in step V and write an equation for the
reaction.
(h) Explain the importance of step V in industries.
(i) Write the formula of solid T.
Name the type of reaction that produces solid T.
5. The flow chart below shows how sulphuric(IV) acid is produced on a large
scale.

Identify:
(i) Gas E
(ii) Solid D
(iii) Gas F
(iv) Substance G
(v) Liquid H
(b) (i) Name the catalyst used in the catalytic chamber.
(ii) Write an equation for the reaction taking place in the catalytic
chamber.
(c) State and explain what you would observe if concentrated sulphuric(VI)
acid is added to:
(i) Cane sugar.
(ii) Copper sulphate crystals.
(d) State one industrial use of sulphuric(VI) acid.
6. The diagram below shows an incomplete set up for the laboratory
preparation and collection of sulphur(IV) oxide gas. Study it and answer the
questions that follow.
(a) Complete the set up to show how dry sulphur(IV) oxide gas may be
collected.
(b) Name:
(i) Liquid A
(ii) Solid B
(c) State the observations made in the reaction vessel.
(d) Write an equation for the reaction between liquid A and solid B.
(e) State and explain the observations that would be made when a piece of
burning magnesium ribbon is dropped into a gas jar containing
sulphur(IV) oxide.
 Chapter Chlorine And Its
6 Compounds

By the end of this Chapter, the learner should be able to:

(a) Describe and explain the laboratory preparation, properties and uses of
chlorine gas.
(b) Describe and explain the laboratory preparation, properties and uses of
hydrogen chloride gas.
(c) Explain the effect of a solvent on the properties of hydrogen chloride.
(d) Describe the industrial manufacture of hydrochloric acid.
(e) Explain the environmental pollution caused by chlorine and chlorine
containing compounds.

Chlorine is a non-metallic element, a halogen in group VII of the periodic table.

The electronic arrangement of the atom is 2.8.7. It forms a diatomic molecular
gas, chlorine. Chlorine does not occur freely due to its reactivity. It is always
found combined with other elements. The chief source of chlorine is sodium
chloride. Sodium chloride is found in sea water and is known as rock salt.

Experiment 6.1: How is chlorine prepared in the laboratory?

Place three spatulafuls of manganese(IV) oxide in a flask. Assemble the
apparatus as shown in figure 6.1. Add concentrated hydrochloric acid drop wise
and collect several gas jars of the gas produced and preserve.
Fig 6.1: Laboratory preparation of chlorine gas.

Answer the following questions

1. State the role of the following in the set-up:
(a) Manganese(IV) oxide.
(b) Water.
(c) Concentrated sulphuric acid.
(d) Moist blue litmus paper.
2. Name the method of collection used in the set-up. Explain.
3. Write a balanced chemical equation for the reaction between concentrated
hydrochloric acid manganese(IV) oxide.
4. Suggest other reagents that could be used instead of manganese(IV) oxide.

Discussion
Chlorine gas may be prepared in the laboratory by the oxidation of concentrated
hydrochloric acid with a suitable oxidising agent such as manganese(IV) oxide.
MnO2(s) + 4HCl(aq) MnCl2(aq) + 2H2O + Cl2(g)

Heating speeds up the reaction between manganese(IV) oxide and concentrated

hdryochloric acid. Chlorine can also be prepared by other methods such as
oxidation of concentrated hydrochloric acid by potassium manganate(VII) or
lead(IV) oxide.
16HCl(aq) + 2KMnO4(s) 5Cl2(g) + 2MnCl2(aq) + 8H2O(l) +
2KCl(aq)
 or
PbO2(s) + 4HCl(aq) PbCl2(s) + Cl2(g) + 2H2O(l)

In these reactions, concentrated hydrochloric acid acts as a reducing agent and is

itself oxidised to water and chlorine. During the preparation of chlorine, the gas
is passed through water to remove the more soluble hydrogen chloride gas.
Vapourised from the hydrochloric acid by the heat. It is then passed through
concentrated sulphuric(VI) acid to be dried. Dry chlorine is collected by
downward delivery (upward displacement of air) because the gas is denser than
air.
The purpose of the blue litmus paper in the experiment is to show when the
gas jar is full of chlorine. When the gas jar is full, the blue litmus turns red then
white. Chlorine is not collected over water because it is soluble in water.

Physical Properties of Chlorine

Experiment 6.2: What are the physical properties of chlorine?
Use the chlorine gas preserved from experiment 6.1 to perform the following
tests. Record your observations in table 6.1.
Table 6.1: Properties of Chlorine Gas

Test Observation

Examine chlorine gas and take note of its colour and smell. Do
not smell chlorine gas directly.
Invert a gas jar of chlorine in a trough of water and allow it to
stand for some time.

Answer the following questions

1. State some physical properties of chlorine.
2. Chlorine is collected by upward displacement of air. Explain.

Discussion
Chlorine is a green-yellow gas with an unpleasant chocking and irritating smell.
It is denser than air and this makes it possible to collect the gas by downward
delivery (upward displacement of air). Chlorine is fairly soluble in water. At 0
°C. 1 volume of water dissolves 3 volumes of the gas. This explains why the
level of water rises inside the gas jar. When inverted in a trough of water.
Chemical Properties Of Chlorine

Experiment 6.3: How does chlorine react with water?

Set the apparatus as shown in experiment 6.1. Prepare chlorine gas and carry out
the following tests.

Test Observations

1. Bubble chlorine gas through water in a boiling tube for a

few minutes. Note the colour of the resulting solution. Place
litmus paper in the solution.
2. Collect 3 gas jars of dry chlorine:
(a) Place dry blue and red litmus paper in the first jar.
(b) To the second gas jar, place moist red and blue litmus
papers.
(c) To the third gas jar, place fresh coloured flower petals.

Answer the following questions

1. What is the colour of the solution formed when chlorine is bubbled
through water.
2. Write the equation for the reaction between chlorine and water.
3. What observations were made when:
(a) Dry blue and red litmus papers were placed in chlorine?
(b) Moist litmus papers and fresh coloured flowers were placed in
chlorine? Explain.
4. Write an equation to show the effect of chlorine on dyes.

Chlorine reacts with water forming both chloric(I) acid, (hypochlorous acid) and
hydrochloric acid. This green-yellow solution is commonly referred to as
chlorine water and is acidic.
Cl2(g) + H2O(l) HOCl(aq) + HCl(aq).
Moist blue litmus paper placed in a gas jar full of chlorine first turns red and is
then decolourised (bleached). Coloured flowers are decolourised too. The
chloric(I) acid formed when chlorine dissolves in water is not a stable
compound. It readily gives up its oxygen atom (nascent oxygen, especially when
exposed to sunlight). In the process the green yellow solution looses colour.

When mixed with dyes, the free oxygen atom released by chloric(I) acid
readily combines with the dyes to form colourless matter.
Dye + HOCl(aq) HCl(aq) + colourless matter

This explains the bleaching action of chlorine. Chlorine bleaches by oxidation.

Bleaching by oxidation is long lasting as compared to bleaching by reduction.
However, dry chlorine has no effect on litmus paper and dyes if materials are dry
because chloric(I) acid does not form.

Experiment 6.4: How does chlorine react with metals?

Set the apparatus as in figure. 6.1. Collect dry chlorine gas in two gas jars. Pass
dry chlorine gas over hot iron wire as shown in figure 6.2. Record your
observations. Use the gas collected to carry out the following tests and record
your observations in table 6.2.
Fig 6.2: Reaction of chlorine with metals

Table 6.2: Reaction of chlorine with metals

Test Observation

1. Lower a piece of burning magnesium in a gas jar of chlorine.

2. Repeat the test using hot iron wire instead of burning

magnesium.
3. Pass dry chlorine gas over hot iron wire coil in a combustion
tube as shown in figure 6.2.

Answer the following questions

1. What observations were made when:
(a) Burning magnesium was lowered into a gas jar chlorine?
(b) Hot iron wire was lowered into a gas jar of chlorine?
(c) A stream of dry chlorine was passed over a hot iron wire coil?
2. Write balanced chemical equations for the reactions between chlorine and
the metals.

Discussions
Burning magnesium continues to burn in chlorine gas forming white fumes of
magnesium chloride.
Mg(s) + Cl2(g) MgCl2(s)
Magnesium continues to burn because the heat produced sustains the reaction.
When hot iron is lowered into a gas jar full of chlorine, the wire starts to glow.
The wire continues glowing as black crystals of iron(III) chloride are formed.
2Fe(s) + 3Cl2(g) 2FeCl3(s)
The glow continues for a long time because the reaction between iron and
chlorine is exothermic. When dry chlorine is passed over a hot iron wire coil as
shown in figure 6.2, the iron(III) chloride formed collects in the flask as a
sublimate.
Anhydrous calcium chloride allows dry chlorine fumes to escape and also
prevents the entry of moisture. Calcium oxide may be used to replace calcium
chloride because being basic, it reacts with the acidic chlorine gas to form a salt,
thus, preventing air pollution.
Where a metal has more than one oxidation state, the chloride of the metal
with the higher
oxidation number is formed. Thus iron(III)
chloride is formed rather than iron(II) chloride. Generally, chlorine reacts with
most metals when hot to form the corresponding chloride.

Experiments 6.5: How does chlorine react with non-metals?

Place a piece of dry red phosphorus on a deflagrating spoon and warm. Lower
the warm piece of phosphorus into a gas jar of chlorine. Record your
observation.

Answer the following questions

1. What was observed when warm red phosphorus was lowered into a gas of
chlorine gas?
2. Write the equation for the reaction between phosphorus and chlorine.

Discussion
When a piece of warm red phosphorous is lowered into a gas jar of chlorine a
vigorous reaction takes place producing white fumes. The white fumes are a
mixture of phosphorous(III) and phosphorous(V) chloride.
P4(s) + 6Cl2(g) 4PCl3(s)
P4(s) + 10Cl2(g) 4PCl5(s)
Chlorine and hydrogen do not react at room temperature. However, when a jet of
burning hydrogen is lowered into a jar of chlorine gas, combustion continues and
white fumes of hydrogen chloride are seen at the mouth of the jar. This is done
under special conditions which will be studied later in this chapter under large
scale manufacture of hydrochloric acid.

Caution:
Reaction between chlorine and white or
yellow phosphorus should be avoided as
these are highly flammable. The
reaction between chlorine and hydrogen
is very dangerous and should be
avoided too.

Oxidising Properties of Chlorine

Experiment 6.6: How does chlorine react with reducing agents?

Using chlorine from a source as shown in figure 6.1, perform the following
experiments and record your observations in table 6.3.
Table 6.3: Reactions between chlorine and hydrogen sulphide, sulphites and ammonia.

Test Observation

1. Bubble chlorine gas through sodium sulphite solution in a

beaker for a few minutes. Put 2 cm3 of the resulting
solution into two separate test-tubes, labeled A and B.
(a) To test-tube (A), add a few drops of dilute nitric acid
followed by a few drops of barium nitrate solution.
(b) To test-tube (B), add a few drops of lead nitrate
solution. Warm the mixture.
 2. Bubble chlorine gas through aqueous ammonia.

Answer the following questions

1. What observations were made when:
(a) Barium nitrate solution was added to acidified solution in test (a)?
(b) Lead nitrate solution was added to the solution in test (b)?
2. Write ionic equations for the reactions in tests 1(a) and 1(b).
3. What observations were made when chlorine was bubbled through
aqueous ammonia? Write an equation for the reaction.

Discussion
When barium nitrate is added to an acidified solution of sodium sulphite through
which chlorine has been bubbled, a white precipitate is formed. The white
precipitate confirms the presence of sulphate ions. Chlorine is a strong oxidising
agent and oxidises many substances. When bubbled through a solution of
sodium sulphite, chlorine oxidises the sulphite ions to sulphate ions.
Cl2(g) + Na2SO3(aq) + H2O(l) 2HCl(aq) + Na2SO4(aq)
or

When barium nitrate is added to the mixture, the barium ions combine with the
sulphate ions to form insoluble barium sulphate.

The solution is first acidified before barium nitrate solution is added to eliminate
the possibility of sulphite ions. When lead(II) nitrate is added to the solution
formed by bubbling chlorine gas through sodium sulphite solution, a white
precipitate is formed. The white precipitate does not dissolve on warming. This
confirms the presence of sulphate ions.

Any precipitate of lead(II) chloride formed dissolves when the mixture is

warmed. Chlorine reacts with ammonia to form white fumes of ammonium
chloride.
8NH3(g) + 3Cl2(g) 6NH4Cl(s) + N2(g)
When chlorine is mixed with moist hydrogen sulphide gas, a yellow deposit of
sulphur is seen in the gas jar. Chlorine oxidises sulphide ions in the moist
hydrogen sulphide to pale–yellow solid sulphur.
H2S(aq) + Cl2(g) S(s) + 2HCl(g)

Reaction of Chlorine with Alkaline Solutions

Experiment 6.7: How does chlorine react with alkalis?

Perform the following tests and record your observations in table 6.4.
Table 6.4: Reaction between chlorine and alkalis

Test Observations

Bubble chlorine gas into cold dilute sodium hydroxide

solution.
Repeat the experiment using hot concentrated sodium
hydroxide.

Answer the following questions

1. What is observed when chlorine is bubbled through:
(i) Cold dilute sodium hydroxide?
(ii) Hot concentrated sodium hydroxide?

Discussion
The product formed when chlorine reacts with alkalis depends on the
temperature and concentration of the alkali. Chlorine reacts with cold dilute
sodium hydroxide or potassium hydroxide forming a pale-yellow solution of
chlorite(I) and the chlorides of the respective metals.
Cl2(g) + 2NaOH(aq) NaOCl(aq) + NaCl(aq) + H2O(l)
Cl2(g) + 2KOH(aq) KOCl(aq) + KCl(aq) + H2O(l)
With hot concentrated sodium or potassium hydroxide, the respective metal
chlorate(V) and chlorides are formed.
6NaOH(aq) + 3Cl2(g) NaClO3(aq) + 5NaCl(aq) + 3H2O(l)
6KOH(aq) + 3Cl2(g) KClO3(aq) + 5KCl(aq) + 3H2O(l)
A similar reaction takes place when chlorine is bubbled through solutions of
calcium hydroxide.
2Ca(OH)2(aq) + 2Cl2(g) CaCl2(aq) + Ca(OCl2)(aq) + 2H2O(l)
Calcium hypochlorite, Ca(OCl)2, is commonly referred to as bleaching powder.

Experiment 6.8: How does chlorine react with bromides and

iodides?
Perform the following series of experiments and record your observations.

Test Observation

Bubble chlorine gas through potassium bromide solution.

Repeat the experiment using potassium iodide instead of
potassium bromide.

Answer the following questions

1. What is observed when chlorine is bubbled through a solution of:
(a) Potassium bromide?
(b) Potassium iodide?
2. Write:
(a) Balanced equations for the reactions in 1(a) and (b).
(b) Ionic equation for the reactions in 1(a) and (b).
 3. Explain how chlorine acts as an oxidising agent.

Discussion
When chlorine gas is bubbled through a solution containing bromide ions, the
colourless solution turns orange. Chlorine has a higher tendency to gain
electrons than bromine. It therefore readily oxidises bromide ions to bromine.

Ionic equation.
Cl2(g) + 2Br-(aq) 2Cl-(aq) + Br2(aq)
Similarly, when chlorine is bubbled through a solution containing iodide ions,
the colourless solution turns brown. Chlorine oxidises iodide ions to iodine
which in the presence of iodide ions is a reddish-brown solution.
Cl2(g) + 2KI(aq) 2KCl(aq) + I2(aq)
Ionic equation.
Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(aq)
These reactions are examples of displacement reactions.

Note:
Iodine only exists in solution in the
presence of iodide ions.

Test for Chloride Ions

Experiment 6.9: How is the presence of chloride ions tested?

Carry out the following tests and record your observations in table 6.5.
Table 6.5: Test for Chlorides

Test Observation

1. Place a spatulaful of sodium chloride in a boiling tube. Place

 moist blue and red litmus papers at the mouth of the boiling
tube. Add 1cm3 of concentrated sulphuric(VI) acid. Bring a
glass rod dipped in aqueous ammonia above the mouth of
the boiling tube.
2. Prepare 5 cm3 of sodium chloride solution.

(i) To a 2 cm3 portion of the solution add a few drops of

lead(II) nitrate solution.
(ii) Warm the resulting solution from 2 (i).

Answer the following questions

1. What observations are made when concentrated sulphuric(VI) acid is
added to sodium chloride?
2. What observations are made when:
(i) Lead(II) nitrate is added to sodium chloride solution?
(ii) The solution mixture of sodium chloride and lead(II) nitrate solutions
is warmed?
3. Write equations for the reactions between:
(a) Sodium chloride and concentrated sulphuric(VI) acid.
(b) Sodium chloride solution and lead nitrate solution.

Discussion
When concentrated sulphuric(VI) acid is added to sodium chloride crystals,
white fumes are produced. The fumes turn moist blue litmus red. The white
fumes are
hydrogen chloride. To confirm the presence of hydrogen chloride, a glass rod
dipped in ammonia solution is held over the mouth of the gas jar as the gas is
liberated.
Formation of dense white fumes of ammonia chloride confirms the presence of
hydrogen chloride hence chloride ions in the solid substance.

Caution:
 Hydrogen chloride is poisonous. Avoid
inhaling it.

Presence of chloride ions in a solution can be tested with the lead(II) nitrate
solution. In this case, a white precipitate of lead(II) chloride is formed.
Pb(NO3)2(aq) + 2HCl(aq) PbCl2(s) + 2HNO3(aq)
When warmed, the lead(II) chloride precipitate dissolves in the solution. It
however recrystallises on cooling.

Uses of Chlorine and its Compounds

Chlorine and its compounds are put into a wide range of use in industries, some
of these are:
• Manufacture of hydrochloric acid.
• Manufacture of bleaching agents such as sodium chlorate(I) used in the
cotton and paper industries. (See figure 6.3(a))
• Chlorine is used in the treatment of drinking water and in sewage plants.
• Manufacture of chloroform, an anaesthetic.
• Manufacture of solvents such as trichloroethane and some
chlorofluorocarbons (CFCs).

Some common chlorine based bleaching agents

• CFC(s) commonly referred to as ‘freons’ are used as refrigerants in fridges
and air conditioning units due to their low boiling points.
• Compounds of chlorine are used in the manufacture of plastics such as
polyvinyl chloride (PVC).
• Manufacture of germicides, fungicides and pesticides such as DDT and some
CFCs.
• CFCs are used to manufacture aerosol propellants.

Exercise 6.1
1. (a)Write a balanced equation for the reaction which takes place when a
mixture of concentrated hydrochloric acid and solid manganese(IV)
oxide is heated.
(b) A mixture of 1g of solid manganese(IV) oxide and concentrated
hydrochloric acid containing 1g of pure acid is heated in the above
reaction. Calculate the maximum number of moles of chlorine gas that
could be formed.
(Mn = 55, Cl = 35.5, O = 16, H = 1.0).
2. (a) Chlorine is obtained commercially by the electrolysis of fused sodium
chloride.
(i) Write down the equation for the production of chlorine at the
appropriate electrode and name the type of chemical reaction taking
place.
(ii) Give two industrial uses of chlorine.
(b) Explain how the bleaching action of moist chlorine is achieved.
(c) Bromine and iodine are members of the same group in the Periodic
Table as chlorine. Describe tests by which these three members could
be arranged in order of their reactivity.
3. Study the flowchart below and answer the questions below.
 (a) Name:
(i) Solid P
(ii) Gas Q
(iii) Solid T
(iv) Solid U
(b) Write an ionic equation for the formation of the redish brown liquid R.
(c) Give a commercial application of solution S.
(d) State and explain the observation made when a gas jar containing
chlorine gas is inverted over a gas jar containing hydrogen sulphide gas.
4. Give a reason why chlorine is used in the manufacture of pesticides and
germicides.

Hydrogen Chloride
Hydrogen chloride (hydrochloric acid gas) is a compound of hydrogen and
chlorine. It is a molecular substance which exists as a gas at room temperature.

Experiment 6.10: How is hydrogen chloride prepared?

Place four spatulaful of rock salt in a flask. Assemble the apparatus as shown in
figure 6.3. Add concentrated sulphuric(VI) acid drop-wise and collect several
gas jars full of the gas liberated. Use the gas collected to perform the following
tests and record your observations as shown in table 6.6.
Fig 6.3: Laboratory set up for preparation of hydrogen chloride
Table 6.6: Physical Properties of hydrogen chloride gas

Test Observation

1. Invert a gas jar full of hydrogen chloride gas in a trough of

water.
2. Carry out the ‘fountain’ experiment with hydrogen chloride.

3. Place a glass rod dipped in concentrated ammonia solution at

the mouth of a jar of hydrogen chloride.
4. Place moist blue and red litmus paper in a gas jar of
hydrogen chloride.

Answer the following questions

1. What observation is made when a gas jar of hydrogen chloride is inverted
into a trough of water? Explain.
2. What observation is made when ammonia gas comes into contact with
hydrogen chloride gas? Write an equation for the reaction.
3. What is the effect of hydrogen chloride gas on moist litmus paper?
4. Comment on the method of collection of the gas.

Discussion
Hydrogen chloride is a colourless gas with a pungent choking smell. It is denser
than air and is collected by downward delivery (upward displacement of air).
Hydrogen chloride is very soluble in water. When a gas jar full of hydrogen
chloride is inverted into a trough of water, the water rises rapidly in the gas jar.
At 0°C, 1 volume of water dissolves about 500 volumes of the gas. The
‘fountain’ experiment is a more dramatic demonstration of the solubility of the
gas in water.
Hydrogen chloride gas turns moist blue litmus paper red showing that
hydrogen chloride gas is acidic.

Chemical Properties of Hydrogen Chloride

Preparation of aqueous hydrogen chloride

Replace the gas jar in figure 6.4 with a large beaker filled with distilled water to
about three-quarter (¾) its capacity. Fit a filter funnel at the end of the delivery
tube. Arrange the apparatus as shown in figure 6.4. Use the solution prepared to
perform the series of experiments in experiment 6.9.

Figure 6.4: Preparation of aqueous hydrogen chloride.

Bubble hydrogen chloride gas into a boiling tube containing about 20 cm3 of
methylbenzene in a fume cupboard.

Experiment 6.11: What are some of the chemical properties of

hydrogen chloride?
Using aqueous hydrogen chloride solution perform the following tests and
record your observations in table 6.7.
Table 6.7: Some properties of hydrogen chloride

Test Observation

1. Place blue litmus paper in a test-tube containing hydrogen

 chloride solution.
2. (i) Put a piece of zinc metal in a test-tube. Add 5 cm3 of
hydrogen chloride solution. Wait for a while then place a
burning splint at the mouth of the test-tube.
(ii) Repeat experiment (i) above using a half spatula of iron
fillings, 2 cm3 magnesium ribbon or a few pieces of
copper in place of zinc.
3. Put about 5 cm3 of 2 M sodium hydroxide solution in a
beaker. Add two or three drops of phenolphthalein or methyl
orange. Using a dropper, add hydrogen chloride solution
drop - wise until there is no further change.
4. (i) Place a few pieces of marble chips in a test-tube,
containing hydrogen chloride solution. Test the gas
evolved with lime water.
(ii) Repeat the experiment using zinc carbonate, copper
carbonate and sodium hydrogen carbonate.
5. Add a few drops of lead nitrate solution to a portion of
hydrogen chloride solution.
6. Repeat tests 1 to 4 using the solution of a portion of
hydrogen chloride in methylbenzene.

Answer the following questions

1. Why is the glass funnel in figure 6.4 dipped just below the water surface?
2. What observations are made when aqueous hydrogen chloride reacts with:
(a) Metals?
(b) Sodium hydroxide solution?
(c) Carbonates and hydrogen carbonates?
(d) Lead nitrate solution?
Write equations for the reactions in (a) and (b).
3. What is observed when the tests in 2(a) – (d) were done using a solution of
hydrogen chloride in methylbenzene?
 4. What is observed when litmus paper is placed in a solution of hydrogen
chloride in:
(i) Distilled water?
(ii) Methyl benzene?

Discussion
The filter funnel provides a large surface area for the gas to dissolve in the water.
It is dipped just bellow the surface of the water to prevent sucking back.
Hydrogen chloride gas turns moist litmus paper red, indicating that the gas is
acidic. When the gas is dissolved in methyl benzene, it does not exhibit the acid
properties. In aqueous solution, hydrogen chloride dissociates into hydrogen and
chloride ions.
HCl(g) H+(aq) + Cl-(aq)
When hydrogen chloride gas dissolves in water hydrochloric acid is formed.
In methyl benzene, hydrogen chloride gas dissolves but does not ionise. It exists
as molecules. This explains why the solution has no effect on moist blue litmus
paper. Note that it is the presence of hydrogen ions (H+) that gives a solution its
acidic nature. When hydrogen chloride gas comes in contact with ammonia gas,
dense white fumes of ammonium chloride are formed.

This is used as the test for the gas.

All metals above hydrogen in the reactivity series react with hydrochloric
acid liberating hydrogen gas.
Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
Fe(s) + 2HCl(aq) FeCl2(aq) + H2(g)
Very reactive metals such as sodium and potassium react explosively with
hydrochloric acid forming a salt and hydrogen gas.
2Na(s) + 2HCl(aq) 2NaCl(aq) + H2(g)
Copper metal which is below hydrogen in the reactivity series does not react
with hydrochloric acid solution. Hydrogen chloride solution reacts with
carbonates and hydrogen carbonates liberating carbon(IV) oxide (carbon
dioxide) gas.
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
ZnCO3(s) + 2HCl(aq) ZnCl2(aq) + H2O(l) + CO2(g)
CuCO3(s) + 2HCl(aq) CuCl2(aq) + H2O(l) + CO2(g)
NaHCO3(s) + HCl(aq) NaCl(aq) + H2O(l) + CO2(g)
When hydrochloric acid reacts with hydroxides or basic oxides, neutralisation
takes place. A salt and water are the only products of the reaction. The resulting
solution is neutral to litmus.

Large Scale Manufacture of Hydrochloric Acid

In the large scale manufacture of hydrochloric acid, hydrogen and chlorine are
the major raw materials. Hydrogen may be obtained by electrolysis of brine,
cracking of long chain hydrocarbons or reacting methane gas (natural gas) with
steam at high temperature. On the other hand, chlorine may be obtained by the
electrolysis of either fused sodium chloride or brine. In the industrial process, a
mixture of chlorine and hydrogen is burned to form hydrogen chloride gas.
H2(g) + Cl2(g) 2HCl(g)
A mixture of chlorine and hydrogen reacts explosively when heated. To control
the reaction, a small amount of hydrogen gas is allowed to burn in excess
chlorine through a jet as illustrated in figure 6.5.
Figure 6.5: Large scale manufacture of sulphuric acid

The hydrogen chloride gas formed is dissolved in water over glass beads. The
beads increase the surface area over which the gas dissolves in water.
Commercial hydrochloric acid is about 35% pure. Hydrochloric acid is
transported in steel tanks lined inside with rubber. In Kenya, hydrochloric acid is
manufactured on a large scale at Webuye.

Uses of hydrochloric Acid

• Removing rust from metal. For example: de-scaling iron before it is
galvanised, other metals before they are electroplated.
• Treatment of water (chlorination) at the water works.
• Sewage treatment.
• Making dyes, drugs and photographic materials such as silver chloride on
photographic films.
• pH control and neutralisation in industries that require purity.
Exercises 6.2
1. When a mixture of hydrogen and chlorine gas is left in diffused light for
sometime, the green-yellow colour gradually fades and a gas that fumes
with ammonia is formed. If a similar mixture is passed over a hot platinum
wire, the green-yellow colour fades quickly.
(i) Identify the gas that fumes with ammonia gas.
 (ii) What effect does hot-platinum wire have on the mixture of gases?
(iii) Write an equation for the reaction that occurs between hydrogen and
chlorine.
2. Use the reaction scheme below to answer the questions that follow.

(a) Name substances A to H.

(b) Write down the equation for the reaction between solution E and
aqueous silver nitrate.
(c) Describe a test by which you could identify gas F.

Environmental Pollution by Chlorine and its Compounds

Environmental pollution encompasses water pollution, air pollution and land
pollution. Chlorine gas as an element, if allowed into the atmosphere can be
dangerous particularly during the rains. It may dissolve in the rain and fall as
acid rain. Acid rain may have adverse effects on both plant and animal life as
well as on buildings and some nutrients in the soil.
Chlorofluorocarbons (CFC’s or “Freons”) are gaseous organic halogen
compounds that have a wide range of applications in industry and in the
laboratory. They are non-biodegradable and hence have a long life span. For
instance, CCl3F has a life span of 75 years and CCl2F2 has a life span of 110
years.
Over time, CFC’s slowly diffuse into the atmosphere where they break down
into free chlorine and fluorine atoms. The reactions of these free atoms with
other substances under the influence of ultraviolet light accelerate the
disintegration of the ozone layer, (O3). Chlorine gas is therefore classified as one
of the green house gases. The ozone layer prevents ultraviolet radiations from
reaching the earth’s surface where they would have adverse effects on plant and
animal life.
Polyvinylchloride (PVC) plastics are non-biodegradable and are major land
pollutants.
Dichlorodiphenyltrichloroethane (DDT), a pesticide, is a compound of
chlorine. The compound has a long life span and so affects both plants and
animal life. Use of DDT has been restricted to Public Health use in Malaria
control through the International Stockholm Convention. Many other countries,
Kenya included have completely banned the use of DDT. The National
Environmental Management Authority which monitors the environmental
impacts of various activities advises increased use of natural pyrethroids in
mosquito control. Kenya is a leading producer of pyrethrum which is the source
of the pyrethroids.

Summary
1. Chlorine is anon-metallic element belonging to the family of halogens.
2. Chlorine water contains hydrochloric and chloric(I) acid.
3. Hydrochloric acid reacts with metals above hydrogen in the reactivity series
liberating hydrogen gas.
4. Hydrochloric acid reacts with carbonates liberating carbon dioxide gas.
5. Soluble chlorides react with lead nitrate solution to form white lead chloride
which dissolves when warmed.
6. Liberation of hydrogen chloride gas when concentrated sulphuric(VI) acid is
added to a solid is a test for the presence of chloride ions in a solid.
Revision Exercise
1. Coloured flowers placed in a gas jar containing gas X immediately turned
colourless. A solution of gas X formed a white precipitate with silver nitrate
solution. The precipitate was insoluble in nitric(V) acid but dissolves in
excess aqueous ammonia.
(a) What is the identity of gas X?
(b) Write down the equation for the reactions that took place when:
(i) A solution of gas X reacted with silver nitrate solution.
(ii) Aqueous ammonia was added through the resulting solution in (b)
(i).
2. Commercial hydrochloric acid is about 35% by mass. Calculate its molarity
given that at 25°C, the density of the acid is 1.08 g cm-3.
3. Substance M, with a general formula, Cx Hy burnt in chlorine with a red
flame producing a cloud of black specks and a colourless gas G.
(a) State the collective name for compounds to which M belongs.
(b) State the identity of the black specks and the colourless gas G. Give
reasons for the choice of your answer.
(c) Suggest an experiment you would perform to test gas G.
(d) Write a general equation for the reaction between compound M and
chlorine.
4. The following diagram represents a section of the plant for the large scale
manufacture of hydrochloric acid.

(a) Name gases A and B.

(b) State the role of the glass beads in the plant.
(c) Why is gas A introduced into the reaction chamber through a jet?
(d) Write the chemical equation for the reaction between the gaseous
substances represented by A and B.
1,2- dichroroethane (C2H4Cl2)
5. Two solutions containing cations of metals P and Q were separately added to
a solution containing chloride ions. In both cases, a white precipitate was
formed. It was divided into two portions. To the first portion of each, a few
drops of nitric (V) acid were added. The chloride compound of P was
warmed. The chloride compound of Q dissolved while that of P did not.
(a) Identify the ions of metals P and Q.
(b) Write ionic equations for the reactions that occurred when cations of P
and Q reacted with chloride ions.
6. Chlorine is used to treat water in drinking water supply plants, in a process
called chlorination. Briefly explain how it eradicates the micro-organisms
from water.
7. (a) What does the abbreviation CFCs stand for?
(b) State three factors which make chlorofluorocarbons serious gaseous
pollutants.
(c) Name two other forms of environmental pollution.
 SAMPLE PAPERS

Sample Paper 1A
1. State one use of each of the following apparatus in the laboratory:
(i) Desiccator.
(ii) Crucible.
(iii) Deflagrating spoon.
2. (a) A mixture consists of sulphur and iron filings. Explain how a sample of
sulphur can be obtained from the mixture.
(b) A sample of the mixture in (a) was heated in an open crucible.
(i) State what was observed.
(ii) Write an equation for the reaction.
3. Element K (not actual symbol of element) has isotopes with relative
abundances as shown below.
Isotope Abundance %
18.69

81.28

Calculate the relative atomic mass of element K.

4. A crystal of potassium manganate(VII) was placed at the bottom of a trough
of water as shown in the diagram. After 30 minutes, the water in the trough
was coloured purple. Explain the observation.

5. A student measured the pH values of solutions A, B, C, D, and E and

obtained the following results:
 Solution pH Value
A 0
B 5
C 13
D 8
E 7

Which of the substances A to E is:

(i) A strong acid.
(ii) Weak acid.
(iii) Neutral.
(iv) Strong base.
(v) Weak base.
6. The table below gives the first ionisation energies of the alkali metals.
Element 1st ionisation energy kJ mol-1
A 494
B 418
C 519
(a) Define the term ionisation energy?
(b) Which of the three metals is the least reactive? Give a reason.
7. Dry hydrogen gas was passed over a heated oxide of copper weighing 14.3
g. At the end of the experiment 12.7 g of copper and 1.8 g of water were
obtained. Determine the formula of the oxide (Cu = 63.5, O = 16).
8. Below is an illustration of one of the methods used to collect gases in the
laboratory.

(a) Name the method illustrated above.

(b) Give one major characteristic of gases collected by this method.
9. Using dots and crosses to represent electrons, draw diagrams to represent
bonding in:
(i) Hydroxonium ion, H3O+
(ii) Sodium fluoride, NaF
10. Compound M reacts with hydrogen chloride gas to give another compound
whose structure is;

(a) Give the structural formula and name of compound M.

(b) Write an equation for the reaction which takes place between ethyne
and excess chlorine gas.
11. State three ways that can be used to show that water is a compound of
hydrogen.
12. (a) A piece of burning magnesium was introduced into a jar of nitrogen.
State what was observed.
(b) Water was added to the product of the reaction in (a) and the resultant
solution was tested with litmus solution. State and explain what was
observed.
13. A pure sample of Iodine crystals can be separated from its mixture with sand
by heating.
(i) What is observed during heating?
(ii) What property of iodine makes this separation possible?
14. Study the flow chart below and answer the questions that follow:

(a) Write the formula of the anion present in solid N.

(b) Solid N in the flow chart above burns in air with a red flame. Identify
the:
 (i) Cation present in solid N.
(ii) Metal oxide L.
15. Excess sulphur(IV) oxide gas was bubbled through a solution of sodium
hydroxide containing phenolphthalein indicator.
(i) State what was observed.
(ii) Write an equation for the reaction between sulphur(IV) oxide and
sodium hydroxide solution.
16. Study the set up below and answer the questions that follow.

(a) What is brine?

(b) Name two processes that occur for liquid L to be obtained.
(c) Suggest a chemical test for liquid L.
17. State one reagent that can be used to distinguish between each of the pairs of
ions and in each case state what is observed if each ion is treated with the
named reagent.
(a) Pb2+(aq) and Al3+(aq)
Reagent:
Observation:
(b)
Reagent:
Observation:
18. The set up below was used to investigate the effect of an electric current on
molten lead(II) iodide.
 (a) Identify the cathode and anode.
(b) State what is observed at the:
(i) cathode
(ii) anode
(c) Write equations for the reactions at the.
(i) cathode
(ii) anode
19. Carbon(IV) oxide was bubbled through a fairly concentrated solution of
sodium hydroxide and no visible change was observed, but when bubbled
through calcium hydroxide for a short time, a white precipitate was formed.
Explain.
20. Oxygen can be prepared from hydrogen peroxide in the presence of a
catalyst.
(a) Name the catalyst used.
(b) Write an equation for the formation of oxygen gas.
(c) State a test for oxygen gas.
21. In an experiment to study the reaction between steam and magnesium, a
piece of magnesium was cleaned and the experiment carried out as shown in
the diagram.
 (a) Why was the magnesium ribbon first cleaned.
(b) State why the cotton wool was heated.
(c) Identify gas Z.
22. The diagram below shows a set-up for the laboratory preparation of dry
chlorine gas.
(a) Name:
(i) substance P.
(ii) a suitable drying agent.
(b) What property of chlorine makes it possible for it to be collected as
shown in the diagram?
23. 20 cm3 of sodium carbonate solution was reacted completely with 25 cm3 of
a 0.8 M hydrochloric acid according to the equation.

Calculate the concentration of the sodium carbonate solution in grams per

litre.
24. A given volume of gas G diffuses through a membrane in 10 seconds. Under
the same conditions of temperature and pressure, an equal volume of
 oxygen diffuses through the same membrane in 12.5 seconds. Determine the
molecular mass of gas G.
25. A stream of ammonia gas was bubbled in water containing litmus paper as
shown.

(a) Why was an inverted funnel used?

(b) State the observation made during the experiment.
(c) State one property of the gas.
26. Chlorine gas is prepared in the laboratory by reacting a mixture of lead(IV)
oxide and substance H. When dry chlorine is passed over heated iron wool,
a dark brown solid S is formed.
(i) Identify substance H and S.
(ii) Name the drying agent used to dry chlorine gas.
(iii) Explain the observation made when chlorine is bubbled through a
solution of sodium iodide.
27. Draw the structural formula and give the IUPAC names of the following
hydrocarbons.
(a) HCCCH2CH3
(b) CH3C(CH3)2CH3
(c) CH3CHBrCHBrCH(CH3)CH3
28. The electron arrangement of ions of certain elements represented by the
letters P, Q, R and S are:

P2- = 2.8.8
Q2+ =2.8
R+ = 2.8
S =2.8.8
(a) Explain why S is not represented as an ion.
(b) Which element has the largest atomic radius? Explain.
29. If 25 cm2 of sodium hydroxide solution containing 4.0 g per litre of solution
neutralised 50 cm3 of a monobasic acid, HX containing 1.8 g of acid,
calculate the relative formula mass of the acid.
30. Cynogen is a gaseous compound of carbon and nitrogen only. On complete
combustion in oxygen, 250 cm3 of cynogen forms 500 cm3 of carbon(IV)
oxide and 250 cm3 of nitrogen. Determine the formula of cyanogen.

Sample Paper 2A
1. The grid below shows part of the periodic table. Use it to answer the
questions that follow. The letters do not represent actual symbols.

(a) Which of the elements has the highest atomic radius? Explain.
(b) Identify the most reactive non-metal. Explain.
(c) Give the Electron configuration of:
(i) Element S.
(ii) Element Q.
(d) Compare the atomic radius of P and R. Explain.
(e) Give the formula of one stable ion with an electron arrangement of 2.8
which is:
(i) Negatively charged.
(ii) Positively charged.
(f) Given that the atomic mass of W is 40. Write down the composition of
its nucleus.
(g) Write the formula of the compounds formed between:
(i) Element P and S.
(ii) Element R and T.
2. A label on a bottle of hydrochloric acid has the following information,
 density 1.134 gm3 and percentage purity 37 %.
(a) Find the mass of the hydrochloric acid in 1 cm3 of the stock solution.
(b) Find the number of moles of hydrochloric acid in 1 cm3 of the stock
solution.
(c) Determine the molarity of the stock solution.
(d) Determine the volume of stock acid containing one mole of
hydrochloric acid.
(e) Explain how a molar solution can be prepared using the volume of
stock acid obtained.
3. Study the reaction scheme of ethene shown.
(a) Name and draw the structures of substances R, S, T, U and V.
(b) Name process X.
(c) Identify reagent A.

4. Use the flow chart below to answer the questions that follow.
 (a) Name substances A, B, C, D, Gas X.
(b) Name process Q, R and S.
(c) Write chemical equations for the reactions that take place in;
(i) Reaction chamber to produce B and C.
(ii) Step 4
(iii) Step 7
5. The diagram below represents a set-up that can be used to prepare and
collect nitrogen(IV) oxide.

(a) Write a chemical equation for the reaction that takes place in the boiling
tube.
(b) Name gas X.
 (c) What observation would be made in the boiling tube:
(i) During heating?
(ii) On cooling?
(d) What property of nitrogen(IV) oxide gas makes it possible to be
collected by the method above?
(e) When a piece of burning magnesium is lowered into a gas jar
containing nitrogen(IV) it continues to burn.
(i) Explain the observation made in the gas jar.
(ii) Write an equation for the reaction that takes place in(i) above.
(f) What precaution should be taken when preparing nitrogen(IV) oxide
gas? Explain.
(g) Why would copper(II) nitrate not be a suitable replacement of lead(II)
nitrate in the above experiment?
6. The following table shows the composition of atoms of elements W, X, Y
and Z. The letters do not represent the actual chemical symbols of the
elements. Study the table to answer the questions that follow.

(a) Predict the type of structures in elements W, X, Y and Z.

(b) (i) Name the type of bond formed when W and Y react. Explain.
(ii) Write the chemical formula of the compound formed in (b) (i).
(iii) Comment on the electrical conductivity of the compound formed
between W and Y.
(c) Comment on the reactivity of element Z. Give a reason for your answer.
7. The diagram below represents the industrial manufacture of sulphuric(VI)
acid.
 (a) (i) Write an equation for the reaction in which sulphur(IV) oxide gas is
prepared.
(ii) Why is it necessary to keep the gases pure and dry?
(iii) Write an equation for the reaction that takes place in the
converter.
(iv) Describe the process that takes place in chamber G.
(v) Name two major gases that escape into the environment.
(vi) State and explain the harm these gases being to the environment.
(b) I. Complete the table below to show the observations made when
concentrated sulphuric(VI) acid is added to the substances shown.

Substance Observation

Cobalt(II) chloride

Glucose powder

II. Give reasons for the observation made using:

(i) Cobalt(II) chloride crystals.
(ii) Glucose powder.
8. A mixture of ammonium salt and an alkali was heated during an experiment
to produce ammonia gas. The gas was dried and collected at room
temperature and pressure. All the ammonia gas was then reacted completely
with 250 cm3 of 2 M phosphoric acid, H3PO4.
(a) What is an alkali?
(b) Explain why ammonia gas is not collected:
(i) over water.
(ii) by downward delivery.
(c) Ammonia turns moist red litmus paper blue. Which ion is responsible
for this reaction?
(d) One mole of gas occupies a volume of 2400 cm3 at r.t.p. Given the
equation;
3NH3(g) + H3PO4(aq) (NH4)3PO4(aq)
(i) Determine the volume of ammonia gas that was collected in the
above experiment.
(ii) Calculate the maximum mass of ammonium phosphate that was
obtained in this experiment. (P = 31, H = 1, O = 16)

9. The table below shows the titre values obtained when 25 cm3 of acidified
iron(II) sulphate containing 6.28 g of iron(II) sulphate in 250 cm3 solution
was titrated against 0.02 M potassium manganate(VII) solution.

(a) (i) Complete the table by filling in the missing information.

(ii) Determine the average titre volume.
(b) Calculate the number of moles of potassium manganate(VII) used in the
titration.
(c) Calculate the concentration of the iron(II) sulphate given that its molar
mass is 278.
 (d) Calculate the moles of iron(II) ions in 25 cm3 of solution the iron(II)
sulphate solution.
(e) Determine the number of moles of iron(II) ions that react with one mole
of manganate(VII) ions.
(f) Write the ionic equation for the reaction between acidified manganate
(VII) and iron(II) ions.

Sample Paper IB
1. The following figure shows a section of apparatus used in the laboratory for
measuring volume.

(a) Identify the piece of apparatus illustrated.

(b) State the correct reading of the volume shown.
2. A mixture of phenolphthalein and methyl orange was separated as shown in
the diagram.

(i) Name the method used in the separation of the mixture.

(ii) State the colour of methyl orange in this experiment.
(iii) Phenolphthalein is usually colourless. Explain why it is pink in this
experiment.
3. The number of protons and neutrons of atoms A, B, C and D are as given in
the Table.
Atom Number of Protons Number of Neutrons
A 6 6
B 12 12
C 6 8
D 17 20

(a) Which atom represents an element in group(II) of the periodic table?

Give a reason.
(b) What is the mass number of element C?
(c) Identify the type of bond that will be formed when B and D react. Give
a reason.
4. The following table gives sample results from an experiment carried out to
investigate the relationship between the volume of a fixed mass of gas with
its temperature.

(a) Plot a graph of volume (Y-axis) against temperature (X-axis).

Extrapolate the graph to intercept the X-axis.
(b) Determine the volume of the gas at 50°C from the graph.
5. The table below shows the pH values of solutions A, B, C and D

(a) Which solution is likely to be that of magnesium hydroxide?

(b) Select the solution that reacts with calcium carbonate powder. Give a
reason for your answer.
6. (a) An apparatus to investigate the reaction of bromine with zinc was set up
as in the diagram.

(i) State what was observed in the combustion tube.

(ii) Write an equation for the reaction that occurs in the combustion
tube.
(b) The product in (a) was dissolved in water and aqueous ammonia added
drop wise to the solution until in excess. State what is observed.
7. When 17.12 g of sodium nitrate were heated in an open test-tube, the mass
of oxygen gas produced was 1.72 g. Given the equation of the reaction as.
2NaNO3(s) 2NaNO2(s) + O2 (g)
Calculate the percentage of sodium nitrate that was converted to sodium
nitrite. (Na = 23.0, N = 14.0, O = 16.0)
8. A clean sample of steel wool was placed in a test-tube containing some
water droplets and the test-tube inverted over a trough of water. After three
days, the volume of air in the test-tube changed from 20 cm3 to 16 cm3 and
a brown layer formed on the steel wool.
(a) (i) Identify the brown layer on the steel wool.
(ii) Calculate the percentage decrease in the volume of air in the test-
tube.
(b) A little of the brown solid was dissolved in nitric acid and dilute
potassium hydroxide was added drop-wise until in excess.
(i) State what was observed.
(ii) Write an ionic equation for the reaction.
9. The atomic number of carbon and chlorine are 6 and 17 respectively.
 (a) Draw a diagram to show the electron structure of:
(i) Carbon.
(ii) Chlorine.
(b) Which bond would be formed when carbon and chlorine react?
(c) Would you expect the compound in (b) to conduct electricity? Give a
reason.
10. (a) Write the structural formula of ethene.
(b) Ethene is prepared by reacting ethanol with concentrated sulphuric(VI)
acid. State the conditions for the reaction.
(c) Write an equation of the reaction between ethene and one mole of
fluorine gas.
11. Study the following flow chart and answer the questions that follow.

(a) Name:
(i) Metal B.
(ii) Gas C.
(b) Write an equation for the reaction that occurs when gas A burns in the
air.
(c) State the role of gas A in step 1.
12. Nitric(V) acid is manufactured by catalytic oxidation of Ammonia gas.
(i) Name two raw materials, other than ammonia that are used in the
manufacture of the acid.
(ii) Name the catalyst used.
(iii) Write an equation for the reaction between nitric(V) acid and ammonia
gas.
 (iv) State one use of the product in(iii).
13. Copper(II) oxide was found to be contaminated with sodium chloride
crystals and iron fillings. Describe how a sample of copper(II) oxide can be
obtained from the mixture.
14. Excess lead(II) oxide was added to warm dilute nitric(V) acid and the
mixture stirred. After cooling, the mixture was filtered and a solution of
sodium chloride was added to the filtrate.
(a) Write an equation for the reaction between lead(II) oxide and nitric(V)
acid.
(b) State what was observed when sodium chloride solution was added to
the filtrate.
(c) State what is observed when the mixture in (b) is heated.
15. (a) What conditions make it necessary to extract sulphur by the Frasch
process?
(b) Hot air at about 15 atmospheres is forced down through the smallest of
the three concentric pipes in the Frasch process. State two roles of the
hot compressed air.
16. Study the flow chart below and answer the questions that follow:

Name processes: X, Y and Z.

17. Ethanol (CH3CH2OH) and dimethylether (CH3OCH3) are two compounds
with the same molecular mass. Explain why ethanol has a higher boiling
point (78.2 °C) than dimethylether (–24°C).
18. (a) Define the terms:
(i) Electrolyte.
(ii) Electrolysis.
(b) Explain the difference in conductivity between magnesium and molten
magnesium chloride.
19. A student wanted to prepare carbon(IV) oxide gas by reacting dilute
sulphuric (VI) acid with barium carbonate. State and explain the observation
made.
20. When solid potassium manganate(VII) is heated in a boiling tube, a
colourless gas is liberated.
(a) Complete the set up to show how the gas is collected.

(b) Name the colourless gas.

21. The electron arrangement of element X is 2:8:8:2. Element X was placed in
warm water.
(i) State what was observed.
(ii) Write an equation for the reaction between element X and warm water.
(iii) The resultant solution turned methyl orange yellow. Explain.
22. When excess chlorine is bubbled through cold dilute potassium hydroxide,
the resulting solution acts as a bleaching agent.
(a) Write an equation for the reaction between chlorine gas and dilute
potassium hydroxide.
(b) Explain how the resulting solution acts as a bleaching agent.
23. (i) Biogas contains mainly methane gas. Name two raw materials that can
be used to produce biogas.
(ii) Methane burns in air according to the equation:
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
Determine the volume of air that will be required to have 32 g of
Methane gas completely burned.
 (C = 12, H = 1, molar gas volume at r.t.p. is 24000 cm3, percentage
of oxygen in air = 21).

24. A balloon contains 80 cm3 of gas at 30°C and 4 atmospheres. Calculate the
volume of the balloon at 50°C and 2 atmospheres.
25. Study the flow chart below and use it to answer the questions that follow.

(a) Name:
(i) R
(ii) S
(iii) T
(b) Write a balanced equation for the reaction between R and concentrated
sulphuric(VI) acid.
(c) Write a balanced equation for the reaction between T and dilute
hydrochloric acid.
(d) State the role of solid R.
26. A white crystalline sodium salt C when heated with concentrated sulphuric
acid evolves a gas D which turns moist blue litmus paper red. When
manganese(IV) oxide is added to the reaction and the mixture warmed, gas
E was given off.
(a) Name:
(i) Solid C.
(ii) Gas D.
(iii) Gas E.
 (b) State the role of manganese(IV) oxide in the experiment.
27. The set up below was used to prepare a hydrocarbon.

(a) Name solid X.

(b) Give a reason why sand is placed at the bottom of the flask.
(c) Write a balanced equation for the complete combustion of gas Y.
27. The molecular formula of gas R is 28 and its empirical formular is CH2. (C
= 12, H = 1)
(a) Determine the molecular formula of gas R.
(b) Write the equation for the reaction between R and bromine.

28. Determine the volume of 2.0 M NaOH which when diluted to 250 cm3
would produce a 0.8 M NaOH solution.
29. (a) What observations would be made when silver nitrate acidified with
dilute nitric acid is added to a solution of sodium chloride?
(b) Write an ionic equation for the reaction.

Sample Paper 2B
1. Study the information in the table below and answer the questions that
follow:
 C = 12, H = 1
(a) (i) Complete the table by filling the missing information.
(ii) Identify the homologous series to which each hydrocarbon
belongs.
(iii) Draw and name all possible isomers of the formula whose relative
molecular mass is 68.
(b) Propene and propane both decolourise bromine liquid. Explain with the
help of equations how both hydrocarbons decolourise bromine.
(c) (i) Complete the reaction

(ii) State the type of reaction in (i).

2. In the apparatus shown in the diagram, compound M and N are reacted to
produce ammonia gas which is passed to container T where it is burnt.

(a) (i) Name substance M.

(ii) State the role of the cotton wool and calcium oxide.
(iii) Write an equation for the combustion of ammonia gas.
 (b) Explain why a large surface area is required in the preparation of
ammonia solution.
(c) One of the main uses of ammonia is in the production of fertilisers. Two
such fertilisers are ammonium sulphate, (NH4)2SO4 and urea,
CO(NH2)2.
Calculate the percentage of nitrogen in:
(i) Ammonium sulphate.
(ii) Urea.
(N = 14, H = 1, S = 32, 0 = 16, C = 12)
3. Sulphur(IV) oxide reacts with oxygen in the presence of a catalyst to form
sulphur (VI) oxide according to the equation:

(a) (i) Explain why vanadium(V) oxide is used in preference to platinum

as a catalyst.
(ii) State three optimum conditions for the production of sulphur(VI)
oxide.
(b) Sulphuric(VI) acid is a dibasic acid.
(i) Explain the term dibasic acid.
(ii) Write an equation to show how sulphuric(VI) acid dissociates in
water.
(c) Sulphuric(VI) acid reacts with potassium hydrogen carbonate according to
the equation
H2SO4(aq)+ KHCO3(S) K2SO4(aq) + 2CO2(g)+ 2H2O(l)
Calculate the volume of carbon(IV) oxide produced at r.t.p. when 20
cm3 of 0.5 M sulphuric(VI) acid is reacted with excess potassium
hydrogen carbonate. (K = 39, H = 2, C = 12, O = 16, Molar gas volume
is 24 dm3)
(i)State the conditions under which sulphuric(VI) acid reacts with
potassium nitrate.
(ii) State what is observed and write an equation for the reaction.
4. (a) Hydrogen chloride gas is commercially obtained from the reaction
 between hydrogen and chlorine gas. State the sources of hydrogen and
chlorine gas in this process.
(b) (i) Explain why small amounts of hydrogen gas are burnt in excess
chlorine gas during commercial preparation of hydrogen chloride
gas.
(ii) Write an equation for the reaction between chlorine and hydrogen
gas.
(c) Hydrogen chloride gas reacts with lead(II) ions in solution according to
the equation.
2HCl(g) + Pb2+(aq) PbC12(s) + 2H+(aq)
2.4 litres of hydrogen chloride gas was carefully bubbled through 50
cm3 of 1.0 M solution of lead(II) ions at room temperature.
Calculate:
(i) The number of moles of lead ions that reacted.
(ii) The number of moles of hydrogen chloride.
(iii) The mass in grams of lead chloride formed.
(one mole of gas occupies 24 dm3 at r.t.p. Cl = 35.5, Pb = 207)
5. The table below shows some tests which were carried out on a green solid P
and the observations that were made.

Test Observation

(i) P was heated until A colourless liquid condensed on the cooler part
there was no further of the test-tube.
change. A colourless gas which turned aqueous potassium
dichromate(VI) green was given out and a red-
brown residue R was left.

(ii) Chlorine gas was Solution turned from green to yellow.

bubbled through an
aqueous solution of P.
(a) Identify substances P and R.
P..............................
 R..............................
(b)Name a substance that could be used to test for the colourless liquid.
(c)Write an equation for the reaction that occurred in test (i).
(d)Explain the reaction that occurred in test (ii).
(e)An aqueous solution of P was divided into two portions:
(i) To one portion a few drops of acidified barium nitrate was added.
A white precipitate was formed which did not dissolve in the acid.
Identify the anion in P.
(ii) To the second portion, a few drops of hydrogen peroxide were
added, state and explain what was observed.
6. (a) (i) Briefly describe how sodium carbonate powder can be obtained in
the laboratory starting from sodium hydroxide.
(ii) Write equations for the reactions that take place.
(b) Crystals of sodium carbonate decahydrate (Na2CO3. 10H2O) were
exposed to air for about four days.
(i) State what was observed.
(ii) Name the process that took place.
(iii) Write an equation for the reaction that occurred.
(c) A solution of 2 M sodium carbonate is added to 500 cm3 of a 1 M
calcium ions.
(i) State what is observed. Explain.
(ii) Write an ionic equation for the reaction that takes place.
(iii) Determine the volume of sodium carbonate solution that reacts
completely with calcium ions.
7. The figure below is a set up of apparatus for the preparation of hydrogen
gas.
(a) Identify:
(i) X.
(ii) Y.
(b) Write an ionic equation for the reaction between Y and X.
(c) Hydrogen gas was passed over heated copper(II) oxide in a combustion
tube. State the observations made.
(d) Under suitable conditions hydrogen reacts with nitrogen to produce
ammonia. During the reaction heat is produced.
(i) Write an equation for the reaction.
(ii) Explain why the catalyst used in this reaction should be
powdered.
(iii) Explain why concentrated sulphuric(VI) acid is not a suitable
drying agent for ammonia gas.
(e) The table below shows the percentage yield of ammonia at various
temperatures and pressures in the Haber process.

(i) State how the percentage yield of ammonia varies with pressure at
constant temperature.
 (ii) State the temperature and pressure which gives maximum yield of
ammonia.
(iii) State a reason why the temperature and pressure given in (ii)
above are not normally used.
8. Given that 10 g of calcium carbonate react with exactly 100 cm3 of 2 M
hydrochloric acid to liberate 4.4 g of carbon(IV) oxide:
(a) How many moles of calcium carbonate are in 10 g? (Ca = 40, O = 16, C
= 12)
(b) How many moles of hydrochloric acid are in 100 cm3 of 2 M
hydrochloric acid?
(c) How many moles of carbon(IV) oxide are in 4.4 g of carbon(IV) oxide.
(d) What are the products of the reaction between calcium carbonate and
dilute hydrochloric acid.
(e) From your answers to a, b and c write the equation for the reactions.
(f) What volume would the carbon(IV) oxide occupy at r.t.p? (molar gas
volume = 24 dm3)
 Appendices
Naming of some Compounds
The concept of oxidation numbers is used in naming chemical compounds.
Simple compounds containing only two elements are usually named by reference
to the number of their different atoms without stating oxidation numbers. The
more electropositive element is usually named first and other element given an –
ide ending. For example sodium chloride (NaCl). The prefix such as mono-for 1,
di- for 2, tri-for 3, tetra-for 4 and penta-for 5 are used if more than one atom of
an element is involved. For example carbon(II) oxide (CO), carbon(III) oxide
(CO2), disuphur dichloride (S2Cl2) and silicon (IV) tetrachloride (SiCl4).
The systematic names of substances are based on International Union of Pure
and Applied Chemistry (IUPAC) nomenclature. In this system the oxidation
number of the constituent element with variable oxidation number is indicated
by roman numbers in brackets.
The names of some compounds encountered in the Chemistry Course at KCSE
level are given in table 1 to illustrate the IUPAC system of nomeclature.

Formula of Common name IUPAC name

Oxide

N2O Dinitrogen oxide or Nitrous Nitrogen(I) oxide

oxide
NO Nitric Oxide Nitrogen(II) oxide

NO2 Nitrogen dioxide Nitrogen(IV) oxide

SO2 Sulphur dioxide Sulphur(IV) oxide

SO3 Sulphur trioxide Sulphur(VI) oxide

HClO Hypochlorous acid Chloric (I) acid

NaClO Sodium hypochlorite Sodium chlorate(I)

NaClO3 Sodium chlorate Sodium chlorate(V)

 H2SO3 Sulphurous acid Sulphuric(IV) acid

HNO2 Nitrous acid Nitric(III) acid

HNO3 Nitric acid Nitric(IV) acid

CuSO4 Copper sulphate Copper(II)

sulphate(IV)

Na2SO3 Sodium sulphite Sodium sulphate(IV)

FeS Ferrous sulphide Iron(II) sulphide

FeCl3 Ferric chloride Iron(III) chloride

Na2SO4 Sodium sulphate Sodium sulphate(VI)

Table 1
The names of some complex ions often encountered in the KCSE Chemistry
Course are given in table 2.
Table 2

Formula Common name IUPAC name

Cuprammonium ion Tetraamine copper(II) ion

MnO4- Permanganate ion Manganate(VII)ion

Dichromate ion Chromate(VI) ion

Al(OH)4 Aluminate ion Tetrahydroxo aluminate ion

Identification of Cations
Table 3
Addition of sodium hydroxide to the salt solution

Cation A few drops of NaOH(aq) Excess NaOH(aq)

 Mg2+ White precipitate White precipitate
insoluble

Ca2+ White precipitate White precipitate

insoluble

Al3+ White precipitate White precipitate

dissolves

Zn2+ White precipitate White precipitate

dissolves

Fe2+ Green precipitate which turns brown on Green precipitate

exposure to air insoluble

Fe3+ Brown precipitate Brown precipitate

insoluble

Pb2+ White precipitate White precipitate

dissolves

Cu2+ Blue precipitate Blue precipitate

insoluble

Table 4
Addition of aqueous ammonia to the salt solution

Cation A few drops of Excess NH3(aq)

NH3(aq)

Mg2+ White precipitate White precipitate insoluble

Ca2+ No observable No observable change

change
Al3+ White precipitate White precipitate insoluble

Zn2+ White precipitate White precipitate dissolves

 Fe2+ Green precipitate Green precipitate insoluble

Fe3+ Brown precipitate Brown precipitate insoluble

Pb2+ White precipitate White precipitate insolubel

Cu2+ Pale-blue Pale-blue precipitate. Dissolves to form a

precipitate deep-blue solution.

Table 5
Identification of Anions
Add cold dilute hydrochloric acid to the substance (solid) in a clean test tube and
if there is no reaction warm gently.

Observation Gas Inference

evolved

Colourless gas evolved which forms white Carbon(IV) Carbonate or

precipitate with lime water. oxide CO2 hydrogencarbonate

Gas evolved, smells of rotten eggs and Hydrogen Sulphide

blackens lead acetate paper. sulphide
H2S

Colourless gas evolved with a pungent Sulphur(IV) Sulphite

smell which decolourises potassium oxide SO2
manganate (VII).

Table 6
Table Action of heat
Heat a small amount of the substance (solid) in a clean dry test-tube and test any
gas given out.

Observation Gas Inference

evolved

Colourless vapour condensing to Water Hydrated salt,

neutral liquid. vapour hydrogencarbonate
or hydroxide
 Colourless gas which gives white Carbon(IV) Carbonate, oxalate,
precipitate with lime water. oxide CO2 hydrogen carbonate

Colourless gas, relights glowing splint. Oxygen O2 Nitrate, (of

potassium or
Sodium) oxide

With pungent smell, dark brown of gas Nitrogen(IV) Nitrate except those
which turns moist blue litmus paper oxide NO2 sodium and
red. potassium

Colourless, pungent smelling gas which Ammonia Ammonium salt

turns red litmus paper blue. NH3

Table 7
Confirmatory tests for Anions
For most acid radicals various precipitation reactions are used as a confirmatory
tests.

Anion Test Observation

Carbonate Add a dilute acid to suspected carbonate. Gas evolved

formed white
precipitate with
lime water.

Sulphate Add dilute nitric acid, if no precipitate is White precipitate,

formed then add Barium nitrate. insoluble in dilute
hydrochloric hydrochloric acid.

Sulphite Add barium chloride solution and a little White precipitate,

hydrochloric acid to a solution of the salt. soluble in dilute
hydrochloric acid.

Sulphide S2- Add a dilute acid to solid, if a gas is Gas blackens lead
evolved test with lead acetate paper. (II) acetate paper.

Nitrate Add a small quantity of cold, iron (II) A brown ring

 sulphate solution. Gently pour forms at the
concentrated sulphuric acid down the side junction of the
of the tube so that the solution do not mix. two layers (brown
Note: Test-tube should be in a sloping ring test).
position.
Chloride Cl- (i) Add silver nitrate solution to a salt White precipitate,
followed by dilute nitric acid. insoluble in
(ii) Add lead (II) nitrate solution of the excess nitric acid.
salt. White precipitate,
soluble in hot
water (insoluble
in cold water).

The Modern Periodic Table

1 — indicates Atomic number.

H
1.0 — indicates relative Atomic mass.