CHEMISTRY DEPARTMENT

EDO UNIVERSITY
IYHAMO, EDO STATE, NIGERIA

Semester / Session: First Semester 2018/2019

Course Code: CHM 111
Course Title: Introductory Chemistry I
Course Credit: 3
Course Duration: 3 Hours of Lecture per Week
Day of the Week: Wednesday (8.00 - 11.00am)
Course Lecturer: Dr. (Mrs.). Maliki M.
Lecturers’ Office Hours: Dr. (Mrs.). Maliki M. Monday 12:00-2:00pm.

Email: muniratu.maliki@edouniversity.edu.ng
Alternative Email: ellpetangmaliki@yahoo.com

Intended Learning Outcomes

At the completion of this course, students are expected to:

1. Understand the atomic structure and the use of the mole concept in quantitative chemical
calculations.
2. Calculate and utilize solution concentration units such as molarity.
3. Demonstrate understanding of the basic features of the periodic table and be able to
identify and name elements and ions.
4. Demonstrate understanding of the reactivity of elements based on their position in the
periodic table.
5. Understand the concept of hybridisation and prediction of hybrid structure of simple
compounds
6. Balance chemical equations, identify basic types of chemical reactions and predict the
outcome of these reactions.
7. Apply the gas laws to predict behavior of gases and its application in quantitative
problems.
8. Apply the concepts of chemical equilibrium and solve simple quantitative equilibrium
calculations
9. Understand stoichiometric relationships involved in reactions.
10. Understand radioactive chemistry and its applications

COURSE DETAILS:
Week 1-2:Atomic theory and Nature of atoms.
Week 3:Introduction to the periodic table: properties and Electronic configuration.

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Week 4: Stoichiometry: formulae and Equations, Volumetric analysis, redox precipitation and
complexation reactions.
Week 5: States of matter: Gases, Liquids and solids. Gas laws, General gas equations
Week 6: Chemistry of elements in group 1, 2 and 3
Week 7:Electrochemistry and The Nernst equation.
Week 8:Chemical equilibrium
Week 9:Introduction to solution Chemistry:
Week 10:Introduction to nuclear reactions: Radioactivity.
Week 11: Revision
Week 12: Exam

RESOURCES
• Course lecture Notes: http://www.edouniversity.edu.ng/oer
• Books:

 Atkins, P. and Jones, L. (1997). Chemistry: molecules, matter and change, 3rd. Freeman

 Hottzclaw, H.F. and Robinson, W.R. (Ed). (1988). College Chemistry with Qualitative

 Analysis (8th Ed.) Massachusetts, Toronto: D.C. Health and Company

 Earl, B. and Wilford L.D.R (Eds). (2001). GCSE Chemistry (Revised Ed.). London: John
Murry (Publishers) Ltd.

 Earl, B. And Wilford, L.D. R. (2001). Further advanced chemistry. London: John Murray
(Publishers) Ltd.

 Ndiokwere, C.I. and Ukhun, M.E. (2006). First year University inorganic and physical
chemistry, revised edition. Mindex publishing

 Philip Mathew (1992). Advanced Chemistry, 2nd edition. University press, united kingdom

Course Requirements, Examination and Grading:

This is a core course for all Chemistry major students and required for all student in the faculties
of Sciences, Engineering and Medical Sciences. Students Attendance, assignment, presentation
and mid-semester test will form the continuous assessment and a final written examination. A
minimum of 70% attendance is required to write final examination. Where necessary, practical
tests may be given to students which will be graded and form part of the continuous assessment.
The grades will be distributed as given below;

Continuous assessments (Test, Assignments, Group work etc.): 30%

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Final Examination: 70%

Total Score: 100%

General Course Outline:

Atomic theory and Nature of atoms. Introduction to the periodic table: properties and Electronic
configuration. Stoichiometry: formulae and Equations, Volumetric analysis, redox precipitation
and complexation reactions. States of matter: Gases, Liquids and solids. Gas laws. General gas
equations. Electrochemistry and Redox reactions. Chemical Kinetics, rate orders and rate laws.
Chemical equilibrium, Nuclear Chemistry and Radioactivity.

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 CHAPTER 1
ATOMIC THEORY AND NATURE OF ATOMS

Chemistry studies the composition of matter and the changes it undergoes. Matter has been
defined as anything that has weight and can occupy space. All materials are made up of matter.

For centuries, philosopher, chemist and physicist tried to answer the question of what matter was
made up of using a variety of experiments and observations.

1.1 THE EARLY IDEAS OF THE ATOM

In 440BC a Greek philosopher named Democritus came up with a conceived idea that matter
was composed of very tiny and indestructible particles. He stated that these particles were the
smallest unit of matter which he called atomos – meaning indivisible in Greek. The theory was
not generally accepted because it was a mere philosophy (guess). In 1803, John Dalton proposed
the atomic theory as follows:

1. All elements are composed of atoms and atoms are indivisible and indestructible particles
2. Atoms of the same elements are exactly alike (identical) in size, shape, mass and
chemistry. While atoms of different elements are different.
3. Atoms combine with atoms of other elements in simple whole-number ratios to form
chemical compounds.

Dalton‟s atomic theory became one of the foundations of chemistry and the dawn of
quantitative analysis, because soon after the theory, scientific investigation became rapid.
Curiosity and the urge to understand the world became increased.

1.2 JOSEPH JOHN THOMSON ATOMIC MODEL

Discovery of the electrons
In 1897, J.J. Thomson discovered the electrons while investigating the electrical conductivity of
gases at very low pressure. In his experiment, a very high potential difference (pd) was placed
across a glass tube containing gas at a very low pressure. At that experimental condition, a glow
coming from the negative terminal was observed and it was attracted to the anode. A hole in the
anode allowed the rays to pass through and hit the end of the glass tube‟s surface. The rays was
deflected to the north pole by the magnetic field in the glass tube. The beam hit the fluorescent
screen at the positively charged plate, when it was exposed to an electric field. However, in the
absence of both the magnetic and electrical field or when both fields are on such that the fields
cancels each other influence, the beam was not deflected, it travelled in a straight line and hit the
fluorescent screen at point directly opposite the source.
Thomson concluded that the special ray must be negatively charged because it was attracted to
the positively charged plate and moved away from the negatively charge plate. His conclusion
was supported by the electromagnetic theory which state that a moving charged body behaves

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like a magnet which interact with the electric and magnetic field through which it passes. From
his experiment, Thompson was also able to show that the ray was the same irrespective of the
type of gas in the tube or the type of metal used as the electrodes, stating that the ray must be
inside every atom. The glass tube Thompson used in his experiment is also called the cathode
ray tube, while the negatively charged ray that he discovered are now known as electrons.
Properties of the cathode rays;
1. They are identical irrespective of cathodes (different metals) or gas used in the
experiment, all produced same results.
2. The rays are deflected by magnetic and electric fields.
3. The rays produced some chemical reactions similar to those produced by light.
4. They travel in a straight line when it is not interfered with.

Also, from J.J. Thompson‟s investigation he showed that at ordinary pressure gases are
electrical insulators, but at pressure below 0.01amt, when subjected to a high voltage, gases
break down and conduct electricity.

Based on the knowledge he obtained from the cathode ray experiment- that is the effect of
electric and magnetic field on negatively charged particles, J.J. Thompson was able to derive the
ratio of electric charge to mass of an electron as -1.76 X108 C/g. Where C = Coulomb. Also, a
scientist called R.A. Millikan conducted a number of experiments in 1916 and found the charge
of an electron to be -1.60 X 10-19C. Finally, the mass of the electron was calculated from the
data obtained by J.J. Thompson‟s and R.A. Millikan.

Mass of an electron = charge

Charge/mass

= -1.60 X 10-19
-1.76 X108 C/g.

9.09x 10-28g

FIGURE 1.1 THE CATHODE RAY TUBE

By the early 1900s,it became clear that ccathode rays have identical properties regardless of the
element used to produce them. Also, that all elements must contain negatively charged electrons
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and atoms are neutral. Therefore, there must be positive particles in the atom to balance the
negative charge of the electrons. Thus J.J. Thompson later proposed a revised model for the atom
called the plum pudding model. This is shown in figure 1.2. He describe an atom as a uniform
positive shpere of matter ( the dough) in which negatively charged electrons (raisins) were
stucked.

FIGURE 1.2 THE PLUM – PUDDING MODEL

1.3 RUTHERFORD EXPERIMENT

Discovery of the nucleus
In 1910, Hans Gieger and Ernest Marsden under the supervision of Ernest (later Lord)
Rutherford discovered the nucleus. Streams of positively charged particles were fired at a thin
sheet of gold (gold foil). Rutherford‟s team observed that most of the alpha particles passed
through the gold foil without any deflection at all, while a few of the particles (1:800) were
highly deflected through quite large angle. Sometimes also, but less frequently, α-particles would
bounce back in the direction from which it came. This observation conflicted with Thompson‟s
model, because it was anticipated that since the positive charge in the Thomson‟s atom was
evenly spread out, the beam (α-particle) should have easily passed through the foil with little or
no deflection. Based on this observation, Rutherford proposed that most of the particles passed
through the foil without any deflection because the atom consisted of largely empty spaces and
does not interact much with the α-particles. However, occasionally one of the α-particle
interacted with the very dense positively charged center which he called the nucleus and the very
large repulsion of this positive charged particle and the nucleus resulted in the large deviation in
the path of the α-particles, even to the extent of deflecting the α-particle along the direction from
which it came. This model was clearly different from Thompson‟s.

Rutherford‟s model though very useful, it could not adequately explain the arrangement of
electrons round the nucleus nor did it answer the question of what prevented the electrons from
falling into the nucleus. This is because unlike charges attract and according to classical physics
a moving charged body continually loses energy while it spirals inwards and finally collapses
into the middle. Rutherford model of an atom fail to explain why electron in a given atoms do
not collapse into the nucleus when in motion and could not explain the position and arrangement
of electrons around the nucleus.

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 FIGURE 1.3 RUTHERFORD EXPERIMENT (EXPECTED AND ACTUAL
RESULT)

FIGURE 1.4 RUTHERFORD’S MODEL

1.4 CHADWICK EXPERIMENT

Discovery of the neutrons
After a series of experiments were conducted it was suspected that another type of subatomic
particle exists. For example, experimental observations show that the mass of an oxygen atom
was 16 times larger than the proton and oxygen has only eight positive charges, therefore,
accounting for the remaining mass of the atom became a puzzle.

This puzzle was unraveled by James Chadwick in 1932. In his experiment, Chadwick bombarded
a sheet of beryllium foil with alpha-particles and unknown radiation was produced. The result
from the experiment showed that the particles emitted from beryllium consisted of electrically
neutral particles with mass slightly higher than the proton.

1.5 THE MODERN ATOMIC MODELS

Two atomic models are in use today, they are; the Bohr atomic model and the quantum
mechanical model. Of these two models, the Bohr model is simpler and relatively easy to

7
understand. However, because of some shortcomings of the Bohr model, the quantum
mechanical model is more valid.

1.5.1THE BOHR’S MODEL OF THE ATOM

In 1913, a Danish physicist Niels Bohr (1885 – 1962) proposed an improvement to Rutherford‟s
model. Bohr explained the arrangement of electrons in an atom and provided answers to what
prevented the electrons from falling into the nucleus. He proposed that although the electrons are
negatively charged and the nucleus positively charged, the movement of the electrons in definite
concentric circular path around nucleus prevented the electrons from collapsing into the nucleus.
The concentric circular path (orbit) that the electron orbits is much like the planet orbit around
the sun. The orbits are located at certain fixed distances from the nucleus. Bohr based is
explanation of the atomic model and the electronic energy levels of atoms on the experimental
observation of the emission spectrum of light by atoms.

FIGURE 1.5 THE BOHR’S ATOMIC MODEL

1.5.2 ELECTROMAGNETIC SPECTRUM

Bohr based his explanations on the electromagnetic spectrum. When a white light source or
emitted radiation is passed through a prism, the light splits from its source into series of coloured
bands called spectrum. Atoms also give rise to spectrum called the atomic spectrum.
Electromagnetic spectrum is the entire distribution of electromagnetic radiation according to
frequency and wavelength. It is the entire range of lights that exist and they all travel at the same
speed of light in vacuum (3 x 108 m/s).

Atoms of an element absorb energy when heated, by passing its gas or vapour through an electric
discharge, the atoms become excited and the electron are promoted to a higher energy level. On
falling to their lower energy states lose energy and emit light. The colours are characteristics of
the element, for example hydrogen is red, and sodium is orange and so on.
Each line in an emission corresponds to a discrete (separate) wavelength, frequency and energy
and thus the pattern of lines in the spectrum of each element is unique (like a finger print) to that
element and thus can be used in the qualitative and quantitative identification of elements. Since

8
the wavelength of the emission spectrum tells us what the sample is and the intensity of each
wavelength can tell us how much of the element is present.
Since all electromagnetic radiation have the same speed (i.e. speed is constant), then frequency
of radiation relating to spectral line of wavelength (λ) is giving by the equation;
ƒ=
ƒλ = c
As can be seen from the equation, the wavelength of light increases as the frequency decreases
ƒ (or v) = frequency of radiation express as hertz (Hz) is equivalent to cycle “per second”
c = speed of light (3 x 108 m/s.)
λ = wavelength

The work of Max Planck has also showed that electromagnetic radiation may be regarded as
stream of particles called photon. The energy carried by a photon is related to its frequency by
the expression;

E = hƒ
but ƒ =

Therefore, E =

Where h = Planck‟s constant with a value of 6.63 X 10-34 j-sec. A single photon carries one
quantum of energy.

Example1.1 Calculate the frequency of radiation having a wave length of 6.5 X 10-7meters.

Solution: ƒ =
c =3 x 108m/s
λ= 6.5 X 10-7m

ƒ= = 4.6 x 1014 hertz

Example1.2 Calculate the frequency and energy of a photon having a wave length of 1. 7µm.

Solution: ƒ =
c =3 x 108m/s
1micrometer = 10-6m
1.7micrometer = 1 .7 X 10-6m

λ= 1.7 X 10-6m

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 ƒ= = 1.77 x 1014 hertz

E = hƒ
ƒ = 1.77 X 1014 hertz
h = 6.63 X 10-34 j-sec

E = 1.77 X 1014 X 6.63 X 10-34

E= 1.174 X10-19j

1.5.3 BOHR’S MODEL OF THE HYDROGEN ATOM

Bohr based his theory of the hydrogen atom on the electromagnetic spectrum that hydrogen
produces. At room temperature, hydrogen gas does not emit light but when electricity is
passed through a discharge tube containing hydrogen gas, the molecules break down into
atoms and the tube glows with a reddish pink light. The emission spectrum reveals that the
atom emits radiation in the form of lines. Several series of discrete lines with each
corresponding to a different wavelength in the electromagnetic spectrum are observed. Figure
1.7 shows the emission spectrum of atomic hydrogen.

FIGURE 1.6: THE ATOMIC HYDROGEN SPECTRUM, SHOWING THE FIRST FIVE
SERIES OF THE SPECTRAL LINES.

It can be observed from the spectrum that the intensity and distance between the lines decreases as the frequency
increases after which a continuum is observed. That is the lines in each series become more closely spaced at
increase frequency (decreasing wavelength)
The wave length (λ) of the radiation is related to the frequency (ƒ) by the equation
λ=
ƒ (or v) = frequency of radiation express as hertz (Hz) is equivalent to cycle “per second”
c = speed of light (3 x 108 m/s.)
λ = wavelength (m)
In spectroscopy, frequency is expressed as wave number ( ) and the wave number is the
reciprocal of wave length. = ( ) m-1
Calculating the wavelength of the spectral lines of the hydrogen atom is done by using an
expression giving by Rydberg and therefore known as Rydberg equation:

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 Frequency ( ) = ( ) = R ( )

Where:
n1= quantum number corresponding to the initial energy level (Start).
n2=quantum number corresponding to the final energy level.
R is the Rydberg Ritz constants= 10967876m-1

TABLE1.1 THE FIVE SERIES OF LINES IN THE SPECTRUM OF HYDROGEN

ATOM

Order Series Converge toward n1 n2

First series Lyman series. Ultraviolet region. 1 2,3,4,5,------∞

Second series Balmer series Visible region 2 3,4,5,6,------∞

Third series Paschen series Infrared region 3 4,5,6,7,------∞
Fourth series Brackette. Infrared region 4 5,6,7,8,------∞
Fifth series Pfund series Infrared region 5 6,7,8,9,------∞
It is required that n2> n1 and n values are all integral up to infinity.

Example1.3 Calculate the wavelength of the first, second and third lines in the Lymer series

Solution: Frequency ( ) = ( ) = R ( )

For the Lymer series, n1 = 1 therefore, the first line have n2 = 2, the second line has n2 = 3 and
the third line has n2 = 4. Substituting these values into the Rydberg equation we have;

First line:( ) = R ( )

= 10967876( )

= 10967876( )

= 10967876 X 0.75

= 8225907m-1

λ=( ) = 1.216 X 10-7m

Second line:( ) = R ( )

= 10967876( )

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 = 10967876( )

= 10967876X 0.89

= 9761409.64m-1

λ=( ) = 1.024 X 10-7m

Third line:( ) = R ( )

= 10967876( )

= 10967876( )

= 10967876( )

= 10967876X 0.9375

= 10282383.75 m-1

λ=( ) = 9.73 X 10-8m

Example1.4 Calculate wavelengths and the energy of transition of the second and third lines in
the Balmer series of a hydrogen atom. h = Planck‟s constant = 6.63 X 10-34j/sec, c = speed of
light 3 x 108 m/s

Solution: Frequency ( ) = ( ) = R ( )

For the Balmer series, n1 = 2 therefore, the second line has n2 = 4 and the third line has n2 = 5.
Substituting these values into the Rydberg equation we have;

Second line:( ) = R ( )

= 10967876( )

= 10967876( )

= 10967876( )

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 = 10967876( )

= 10967876X 0.1875

= 2056476.75 m-1

λ=( ) = 4.863 X 10-7m

Energy of transition E =

E=( ) = 4.01 x10-19j

Third line:( ) = R ( )

= 10967876( )

= 10967876( )

= 10967876( )

= 10967876( )

= 10967876 X 0.21

= 2303253.96 m-1

λ=( ) = 4.34 X 10-7 m

Energy of transition E =

E=( ) = 4.58 x10-19j

1.5.4 BOHR’S POSTULATE

The summaries of Bohr‟s postulates are as follow:-
1. The electron moves in circular orbits at different energies around the nucleus.

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 2. The radius of the orbit is quantized. That is orbits are at definite distances from the
nucleus.

3. The electron revolve only in the orbit which have fixed value of energy, thus an electron
in an atom can have only definite or discrete value of energy.

4. As long as the electron remains in a particular orbit, it neither loses nor gain energy.
These orbits are known as stationary state or ground state.

5. If an electron in the ground state (stationary state) with energy Ei, is given sufficient
energy and goes into another allowed orbit, with energy Ef, radiation will be emitted,
with energy and frequency. hƒ = Ei - Ef

1.5.5 THE LIMITATIONS OF BOHR’S ATOMIC MODEL:-

1. It can only explain the line spectrum of an atom with one electron, such as, H atom, He+,
Li2+, Be3+ etc. but unable to explain the line spectra of atoms with more than one electron.

2. It cannot explain the splitting of spectra lines in magnetic field known as ZEEMAN
EFFECT.

3. Bohr‟s model is unable to explain the splitting of spectra lines in an electric field and the
phenomenon is known as STARK EFFECT.

4. Bohr‟s model is also unable to explain Heisenberg‟s uncertainty principles.

1.6 SUBATOMIC PARTICLES

Research studies conducted by Thompson, Chadwick, Rutherford and others reveals that the
atom consist of smaller particles. Also, scientist have been able to discover hundreds of
subatomic particles, however three of these particles; the Proton, Neutron and Electron are of
interest to the chemist.

1.6.1 THE NUCLEUS

The nucleus is the center of the atom and although the size is small compared to the size of the
electron, it accounts for 99.9% the mass of an atom because the proton and neutron are found in
the nucleons. The proton and neutron are called nucleon because they are found in the nucleus of
an atom.

1.6.2 PROTONS, NEUTRON AND ELECTRON

Protons are found in the nucleus of an atom, a proton has a charge of +1, and it is about 1840
times heavier than an electron. Every atom has a specific proton number which tells us the name
of the element. An atom chemical identity is determined by its number of protons. A proton is
what is left after hydrogen atom losses its single electron.

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The neutrons are found in the nucleus. It carries no charge i.e. it is a neutral particle. A neutron
like the proton is considered to have a mass of l amu. The neutrons do not take part in chemical
reaction under normal condition.

Electrons are found outside the nucleus, an electron has a charge of -1. The mass of an electron is
negligible. An electron is approximately the mass of the proton.

TABLE 1.2: THE SUBATOMIC PARTICLES

Particle Symbol Mass (g) Relative Approximate relative
electrical charge mass (a m u)
-28
9.091 x10
Electron e- 1-

Proton p+ 1.67252 x10-24 1+ 1

Neutron n0 1.67495 x10-24 0 1
Note: amu is atomic mass unit

Atoms of an element are electrically neutral, that is they have equal number of protons and
electrons. However, an atom can lose or gain electrons to become an ion. If it gains electron, it
becomes negatively charged and is called an anion. If it losses an electron it becomes positively
charged and is called a cation.

1.7 ATOMIC NUMBER AND MASS NUMBER

The proton number is referred to as the atomic number. The atomic number is the whole
number that increases across each row of the periodic table from left to right. The sum total of
the number of protons and neutrons in the nucleus of an atom is the mass number. If an element
X is represented thus: .

A = Mass number
Z = Atomic number. Therefore
A-Z = Neutron number

1.8 THE RELATIVE ATOMIC MASS

The mass number of an atom cannot be weighed directly because it is very small; however
experimental methods are used to determine the mass of one atom relative to another.
The internationally agreed standard is an atom of carbon-12. This is an isotope of carbon with six
protons and six neutrons, having a mass of 12 atomic mass unit (amu). Based on this standard,
1amu is exactly equal to one- twelfth the mass of one carbon-12 atom ( , the mass of carbon
12). It is because the actual masses of the proton and neutron are very small that for practical
purpose, the atomic mass unit (amu) is used.

Mass of one carbon-12 atom = 12 atomic mass unit therefore,

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 1 atomic mass unit =

The atomic mass unit is related to the number of protons and neutrons. It has nearly the same
value as the mass number.

1.9 THE MASS SPECTROMETER

The process of producing and analysing spectra is called spectroscopy and the instrument for
analysing the spectra is called a spectrometer. The mass spectrometer is an instrument designed
to separate atoms of slightly different masses. First the sample to be separated is vapourized so
as to allow it to move through the machine. The vapourized sample is then hit with high energy
electrons, knocking off one or more electrons thus converting the atoms into positively charged
ions. The ions are accelerated to a higher speed by an electric and magnetic field; also because
ions are charged particles they can be deflected by an electric and magnetic field. The degree of
deflection is thus dependent on the mass to charge ratio. The masses of each particle are
determined by measuring the exact strength of the field and the degree of deflection of the
particles in the mass spectrometer. Different elements have different mass which corresponds to
a different deflection. Figure 1.7 shows the mass spectrometer

FIGURE 1.7: THE MASS SPECTROMETER

1.10 MASS SPECTRA AND ISOTOPES

The proton number (atomic number) tells us what an element is. Every element has its specific
number of proton; however the number of neutrons and electrons may vary. For example carbon
12 has a proton number of 6 and a neutron number of 6 but carbon 14 has a proton number of 6
but a neutron number of 8 with a mass number of 14. This phenomenon is known as isotopy.
Carbon 12 and carbon 14 are known as isotopes of carbon. Thus isotopy is defined as a
phenomenon in which an element has the same number of proton but different number of
neutrons. In other words isotopy is the existence of an element with the same atomic number but
different mass number.
If an element X is represented thus:

A = the mass number (values are different for isotopes)

Z = the atomic number. (Values are same for isotopes) Therefore,
A-Z = Neutron number
Majority of elements found in nature are a mixture of isotopes. For example hydrogen has three
isotopes namely: hydrogen , deuterium and tritium , which is unstable and

16
disintegrates. Almost all hydrogen exists as hydrogen with no neutron. Also, Bromine exists in
nature as and bromine . A mass spectrometer is used to find out the masses of these
isotopes using the carbon -12 scale and the proportion of each isotope. Any naturally occurring
sample of bromine contains approximately 50.52% of , and 49.48% of

1.12 CALCULATING RELATIVE ATOMIC MASSES FROM SPECTRA

The mass spectrum of an element will show the presence of isotopes. From the relative heights
of the peaks, we can work out the relative atomic mass of the element.

Example 4.3: Calculate the relative atomic mass of bromine from the mass spectra of bromine

Solution: Relative abundance of = 50.52%

Relative abundance of = 49.48%

Relative atomic mass = +

= +
= 39.9108 + 40.0788

= 79.9896 9 ≈ 80

1.13 USES OF ISOTOPES

Isotopes have a wide range of uses and it has been used in various aspects of life and nature.

Medicine: Isotopes have been used in the field of medicine as tracers; these are substances
containing a radioactive Isotope of an atom. These tracers are taken up by the organs to be
monitored. For example, Iodine – 131 has been used to study the thyroid function.

Biology: Phosphorus – 32 has been used to study intake of nutrients in plants.

Power Generation: The fission of uranium 235 and the fusion of H – 3 have been used to
create-explosives.

History and Archaeology: Carbon – 1.4 has been used by historians and archaeologist in
determining the ages of ancient remains, such as rocks, bones, plants and so on. This technique is
known as radiocarbon dating.

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PRACTICE QUESTIONS
1. Refute Dalton‟s Theory of “indivisible” atom using J.J. Thompson‟s and
Rutherford Model of the atom.
2. A line spectrum in the hydrogen atom has a wavelength corresponding to 4.57 x 10-7m.
Calculate the frequency and the energy associated with this transition.
3. Calculate the energy of a photon of radiation having a frequency of 3.54 x 1014 hertz.
4. Differentiate between the following;
i. The spectra line of white light and the spectral lines of elements.
ii. Ground state of an electron and the excited state

5. Give reasons for the following:

(i) The nucleus accounts for the mass of an atom.
(ii) The number of protons tells us the name of the element.
(iii) Atomic masses unlike the atomic numbers are not whole numbers.
6. (a) Complete the table below:

Atom or ion of element A B C D E

Mass number 10 - 39 - 19
Number of proton 5 7 - 20 9
Number of neutron - 7 20 20 -

7. What is the atomic mass of chlorine, if has a relative abundance of 75%

and has a relative abundance of 25%

8. Calculate the wavelength the frequency and energy of the lines in the Balmer series
when n2 = 3 and 5

9. The wave number of a line in the Lyman series is 10282383.75m-1

i. Calculate the frequency and energy of the series
iii. Which line in the series is it?

Assume that the atomic mass of an element(X) is 25.77. X has three isotopes; 74.7% of 2613 X,
24.7% of a13 X and 0.6% of 2813 X . Calculate for the value of a

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 CHAPTER 2
THE PERIODIC TABLE

2.1 HISTORY OF THE PERIODIC TABLE

The first classification of elements that became the basis of the present day classification was
done by a Russian chemist called Dimitri Medelev. In 1869 Mendeleev arranged the elements in
increasing atomic weight to form a periodic table. He pointed out that element with similar
properties kept reoccurring at regular intervals or periods, ignoring the fact that some elements
do not follow that order. Mendeleev placed elements with similar properties in horizontal rows,
he called group, while the periods were vertically arranged. He equally left space in his periodic
table for elements that were not discovered yet. Apart from spaces left in Mendeleev periodic
table, his arrangement is different from the modern arrangement of the periodic table.

From his work, Mendeleev proposed a periodic law which states that the properties of the
elements and their compounds vary in a periodic way according to their atomic weight
Mendeleev‟s work was based on the fact that he believed that the only property of an element
which does not change in cause of a chemical combination was its atomic weight. But this is not
true, as it was later discovered from Moseley‟ s work that the atomic number was the only
property in an element that does not change in cause of a chemical combination.

2.3 MODERN PERIODIC LAW

Henry Moseley was able to reveal the atomic numbers of several elements from his study of X-
ray emitted by elements in a discharge tube. Based on his new discovery and the inconsistencies
in the Mendeleev periodic table, Moseley suggested that the elements should be arranged in
order of increasing atomic number instead of atomic mass in the periodic table. Moseley also
proposed the modern periodic law, which states that the properties of the elements vary in a
periodic way according to their atomic numbers.

2.3 INFORMATION FORM THE PERIOD TABLE

In the modern periodic table, classification of elements gives.

19
 1. Elements with similar physical and chemical properties are placed on the same
vertical row called group or family
2. Elements are placed in horizontal row called periods in increasing atomic numbers
from left where the metals are located to the right with the non-metals
3. The table show the symbol of each element, its atomic number its atomic mass and in
some occasion the element‟s electronic configuration
4. The table relates the electronic configuration with the electronic structure and
properties of the element.
5. It shows at a glance the exact period and group an element belongs.
6. The periodic table is divided into 8 groups of elements and 7 periods, with the
transition metals between the group 2 and 3 elements.
7. The periodic table shows the division of elements into metals on the left side and non-
metals on the right hand side of the table.

TABLE 2.1VALENCE SHELL ELECTRONIC CONFIGURATIONS FOR EACH

GROUP

H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca
s1 s2 s2p1 s2p2 s2p3 s2p4 s2p5 s2p6

2.4 REACTIVITY TREND IN THE PERIODIC TABLE

With regards to chemical reactivity, a reaction occurs when element loss, gain or share their
valence electrons with another element or specie. The ease with which elements loss, gain or
share electrons in a chemical reaction measure their reactivity.

Reactivity increases down a metallic group as successive members of the same group increases
by one additional energy level of electrons. Since metals react by loss of electrons, the metals
down the metallic group lose electrons easier than those on top. Therefore lithium is less reactive
than sodium and sodium less reactive than potassium.

On the other hand, non-metals react by gain of electrons, a process called electronegativity. The
more electronegative element is one which gains electrons more easily and is more reactive.
Reactivity (electronegativity) reduces down the group as successive members of the group
increases by one additional energy level of electrons and an increased distance between the
valence electrons and the positive nuclear pull. This makes it more difficult for the positive
nucleus to attract neighboring electrons into the valence energy level, thereby reducing reactivity
as we go down the group. Using the group seven elements as an illustration, fluorine is more
reactive followed by chlorine, bromine than iodine.

20
The period cuts across all the groups in the periodic table. As one moves across a particular
period from left to right, there is increase electronegativity of the element. Since the element
advance toward elements with more electronegative properties

2.5 GROUP OF ELEMENTS

In going down a particular group, it is observed that the elements have similar chemical
properties. This property is directly related to the electronic configuration as each group of
elements has the same number of valence electrons.

2.5.1 GROUP 1 ELEMENT

They are the most electropositive metals. They have one valence electron which they loss in
cause of a chemical reaction.

The members are generally referred to as alkali metals because their hydroxides are soluble.
They react vigorously with cold water, forming an alkali solution and liberating hydrogen gas.
2Na + 2H2O 2NaOH +H2

2.5.2 GROUP 2 ELEMENTS

The Group 2 elements are also called the alkaline earth metals. They are less electropositive than
the group one metals.

They react by loss of two electrons thus divalent.

They react with cold water mildly, given a basic solution that is less soluble than the group 1
elements.
Mg + 2H2O Mg(OH)2 + H2

2.5.3 GROUP 3 ELEMENTS

They are metals which are less electropositive than the Group 1 and 2 elements. They react by
loss of their three valence electrons, thus they are trivalent.

2.5.4 GROUP 4 ELEMENTS

They exhibit non-metallic properties and they are tetravalent because they have four valence
electrons. They form covalent bond by sharing of electrons. There is a gradual change from non-
metallic properties to metallic properties as one move down the group. They exhibit two
oxidation state which are +2 and + 4 oxidation state. The +2 oxidation state increases while the
+4 oxidation state decreases on going down the group.
2.5.5 GROUP 5 ELEMENTS
They are non-metals and show two common valences of 3 and 5. They react by gain of
electrons. Their oxides combine with water to form acid.

2.5.6 GROUP 6 ELEMENTS

Element in group 6 are non-metals. There are electron acceptors and are oxidizing in nature.
They have six valence electrons and require two electrons to reach the octet electron
configuration

2.5.7 GROUP 7 ELEMENTS

21
The elements in Group 7 are known as the halogen which means salt former. They are the most
reactive non-metals known. They are so reactive that they cannot exist free in nature. They react
by gain of one electron.

2.5.8 GROUP 8 ELEMENTS

These elements are also called the noble gases. They are unreactive.

2.5.9 TRANSITION ELEMENTS/METALS

These elements occupy the space between the Group 2 and Group 3 elements on the fourth and
fifth period. They are the element with an incomplete d-orbital.
Also we have the special transition metals on the sixth and seventh periods.
1. The lanthanides series; these are the fourteen elements after lanthanum with atomic
number from 58-71 in the sixth periods. Members successively add one electron to the 4f
sub shell.
2. The actinides series: These are the fourteen elements after actinium with atomic number
from 90-103 in the seventh, periods. Members successively add one electron to the 5f sub
shell.

2.6 PERIODIC PROPERTIES IN THE PERIODIC TABLE

The period properties in the periodic table are all related to the forces of attraction
between the positive nucleus and the negative electrons. These properties include.
1. Ionization energy
2. Electronegativity
3. Electron affinity
4. Atomic radius
5. Ionic radius

2.6.1. Ionizations energy

This is the energy required to remove the most loosely held valence electron or outermost energy
level electron of an atom in the gas phase, to form ions. The ionization energy increases across
the period and decreases down the group. This is because as the group decend, the energy level
increases successively, meaning an increased distanced between the positive nucleus and the
outer energy level electrons. The resultant effect is reduced effective nuclear pull on the
outermost energy level electrons, making the valence electrons easier to remove with reduced
energy.

Ionization energy increases along a period as we go from left to right. Along the period, the
energy level remains the same as electrons are added one after another. This causes shrinkage in
size as the outer energy level electrons becomes more attracted to the positive nucleus, making it
more difficult for electrons to be removed. If the valence electrons become more difficult to
remove, it then means more energy is required (ionization energy) for electron removal. The
table2.2 below summarizes changes in the first ionization energies.

2.6.2. ELECTRONEGATIVITY

22
This is the measure of the ability of an atom to attract electrons when it is in a molecule. In
another word, when two atoms are covalently bonded, sharing a pair of electrons, the atom that
has the ability to attract more of the shared electron pairs is the more electronegative.
Electronegativity increase across the period from left to right. This is because electrons are added
to a constant energy level one after another, with no screening or shielding effect. This causes
shrinkage in size as the valence electrons become more attracted to the positive nuclear pull,
therefore increasing the ability of the atom to attract electrons. As an illustration, in a bond
between carbon and oxygen, oxygen will be more able to attract the shared pair of electron
carbon.
Electronegativity decreases down the group as repeatedly energy level of electrons is added. The
inner energy levels then shield the outer energy level from the attractive pull of the positive
nucleus, thus making it difficult for the atom to attract a shared pair of electrons.
Table 2.3 below summarizes the electronegativity values given on the Pauling's scale using a
value of 4.0 for fluorine.

TABLE 2.2SUMMARY OF FIRST IONIZATION ENERGY DOWN THE GROUPS AND

ACROSS PERIODS

H He
1.3 2.4
Li Be B C N O F Ne
0.5 0.9 0.8 1.1 1.4 1.5 1.7 2.2
Na Mg Al Si P S Cl Ar
0.5 0.7 0.6 0.8 1.0 1.0 1.3 1.5
K Ca
0.4 0.6

TABLE 2.3SUMMARIES OF ELECTRONEGATIVITY TRENDS, DOWN THE GROUP

AND ACROSS THE PERIOD

H He
2.2
Li Be B C N O F Ne
1.0 1.5 2.0 2.6 3.1 3.5 4.0
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.9 2.2 2.6 3.2
K Ca
0.8 1.0
Note that electronegativity values are not assigned to the noble gases
because they commonly donot share electrons

2.6.3. ELECTRON AFFINITY

This is the energy released when an electron is added to a neutral atom in gaseous state to form
gaseous ion.

23
Electron affinity decreases down the group as it become more difficult for electrons to add to an
atom. So, less energy will be released in the cause of the reaction as more energy will be used up.

Electron affinity increases with increase in atomic number along the period as the ease for an
electron to add to a neutral atom becomes less and less difficult. Therefore using less energy for
the reaction and releasing more energy.

2.3.4 ATOMIC RADIUS

An atom does not have a definite diameter; radius, circumference or volume because of its
wave-like nature. Therefore, its size expressed as its radius is done in three different ways, all in
unit of nanometer (nm)

i. Covalent atomic radius: This is the distance from the nucleus to the valence shell when the
sharing of electrons covalently bonds the atom. When the covalent bond involves identical
atoms e.g. H2and O2, the atomic radius is half the distance between the two nuclei

ii. Vander Waals radius: This is half the distance between two nuclei when measured from
their closest point, when no bond is formed.

iii. Atomic radius of metals: This is the distance between nuclei of atom when arranged in a
metal-like crystalline structure.

Atomic radius decrease across a period with increasing atomic number from left to right while it
increases down the group. Table2.4 below give a summary of the trend in atomic radius.

TABLE 2.4ATOMIC RADIUS TREND DOWN THE GROUP AND ACROSS THE
PERIOD

H
He
0.030
Li Be B C N O F Ne
0.123 0.089 0.088 0.077 0.070 0.064 0.064
Na Mg Al Si P S Cl Ar
0.157 0.136 0.125 0.117 0.110 0.104 0.099
K Ca
0.203 0.174

Atomic radius values are not given to the noble gases because they do not form covalent bonds.

2.3.5. IONIC RADIUS

Just like the atoms, ions also have a wave like property which makes their size difficult to

24
ascertain. Ions are formed when atom gain or lose electron(s). The ionic radius is the effective
distance between the nucleus of the ions and its outer energy level. Usually, ions have eight
electrons in the outer energy level.

Metals react by the loss of all their valence electrons, forming positive ions called cation since
all the outer energy level electrons are lost the energy level is lost as well, causing the radius of
the ion to become smaller that the initial atom. Also, greater positive change exerts a greater
attractive force on the electrons, thus causing shrinkage in size

Non-metals on the other hand, react by gain of electrons forming negative ions called anion. The
radius of the ion formed becomes bigger than the initial atom. This is because the electron
gained fill up the energy level, resulting to a greater negative charge. This reduces the attractive
pull of the positive nucleus on the outer energy level electrons. Ionic radius just like atomic
radius increases down the group. But it reduces across the metallic period while it increases
across the non-metallic period.

TABLE 2.5 SUMMARY OF THE IONIC RADIUS TREND DOWN THE GROUP AND
ACROSS THE PERIOD.

H He
0.021
Li Be B C N O F Ne
0.060 0.031 0.020 0.015 0.017 0.140 0.136
Na Mg Al Si P S Cl Ar
0.095 0.065 0.050 0.041 0.212 0.184 0.181
K Ca
0.133 0.099
Reduces Increases
Generally,
1. The ionic radii of positive ions are smaller than their corresponding atomic radii because
increase in positive charge will have a greater nuclear attractive pull on the valence
electrons, causing shrinkage in size.
2 The ionic radii of negative ions are bigger than their corresponding atomic radii because
increase in negative charge will have a reduced nuclear attractive pull on the valence
electrons. Also the increased electrons will have repelling effect on each other causing

25
 increase in size.
3 For Isoelectronic series (ions and atoms with the same number of electrons), ionic radius
decreases as atomic number increase.

ELECTRONIC CONFIGURATION
The electron configuration of an atom is the representation of the arrangement of
electrons distributed among the orbital shells and subshells in its ground state. The physical and
chemical properties of elements are related to their unique electronic configurations. The
valence electrons (electrons in the outermost shell) are the determining factor for the unique
chemistry of the element. Electrons fill up the orbital with lower energy level first before
occupying orbitals of higher energy level. Also, the first orbital or shell will accommodate a
maximum of two electrons after which subsequent orbitals would accommodate a maximum of
eight electrons each. Figure 2.1 shows the electronic configuration of argon with 18 electrons
However, because of some shortcomings of the Bohr‟s model, the quantum mechanical model is
now more valid. The will be treated in the next chapter.

Example 2.1. Do the electronic configuration of argon (atomic number =18).

PRACTICE QUESTIONS
1 a. How is Mendeleev periodic law different from the modern periodic law
b. Mention three information you can get from the periodic table
2. Define the follow and explain their trend down the group and across the period in the periodic
table;

i. Electronegativity
ii. Atomic radius
iii. lonisation energy
3Which noble gas and halogen belong to the third period?

4 List the following atoms in order of increasing electronegativity; K, Al, S, CI, and F

5. List the following in order of reactivity Na, K, Be, and Ca.

6. In the following bonded pairs of atoms, state in each case the atom that attracts more of
bond to itself (a) H: Br (b) Na:CI (c) Mg and Mg2+ (d) CI and CI- (e) K and Ca

26
7. Identify the atom or ion with the larger radius in each of the following pair
(a) S and O
(b) H and Li
(c) Mg and Mg2
(d) Cl and Cl-+
(e) K and Ca

8. Place the following isoelectronic species in order of increasing atomic radii and explain.
Na+, Mg2+, Al3+, Si4+N3-, 02-. F-, Ne

9. Where in the periodic table of the first 20 elements would you expect to find;

(a) The most reactive metals

(b). The most reactive nonmetals
(c). The least reactive metals
(d) The least reactive nonmetals

27
 CHAPTER 3
THE WAVE MECHANICAL MODEL
The wave mechanical model (also called the quantum mechanical model) involves the use of
mathematical equation to describe the arrangement and motion of electrons in atoms.
According to Albert Einstein, light has both wave and particle like character.That is, matter has a
dual nature. A French physicist took up the idea that very small particles such as electrons might
also display wave properties.

In 1926, the Austrian Physicist – Erwin Schrodinger formulated wave-equation to describe the
location and energy of electrons. He incorporated the Bohr, Louis de Broglie and the Heisenberg
uncertainty principle concept and developed the wave mechanical model (Quantum mechanical
model). Unlike the Bohr model, the wave mechanical model does not propose that electrons are
localized in fixed orbits. In fact it does not define the exact location (orbit) of an electron around
a nucleus. It describes the probability of finding can electron in a certain position at any time. If
we assume a cloud of electron round the nucleus, the cloud would be most dense where we have
a greater probability of finding an electron. Such regions where we could find an electron is
called an “orbital”. The electron cloud defines the shape of the orbital.

3.1 ENERGY LEVELS OF AN ATOM

Electrons are arranged in energy level. As we have already known, electrons do not move in
fixed path, the Bohr orbit should not be confused with orbitals.
Electrons with the lowest energy level are found nearer the nucleus while electrons with higher
energy are successively found further away from the nucleus depending on the energy level of
the electron. Each energy level referred to as orbitals have a maximum number of electrons they
can hold, the first energy level which is closest to the nucleus can hold not more than two
electrons. Let us consider the illustration below.

Figure 3.1: Energy level of an atom

3.2 QUANTUM NUMBERS

Quantum numbers are numbers used to completely describe the properties of the electrons
around a nucleus. These properties can be described in terms of four quantum numbers. There
are:

28
Principal quantum number: (n)
This describes the distance of an electron from the nucleus. The number is the same with that
given by Bohr. It describes the size and energy of the orbital. Principal quantum number (n) is
assigned values of integral numbers ranging from n = l, 2, 3, 4 and so on to . The number of
electrons that can occupy a given energy level is given by 2n2. Orbitals with the same n-value are
said to belong to the same energy level or the same shell.

Azimuthal or subsidiary or angular momentum quantum number: ( ).

This number determines the shape of the subshells. The principal quantum energy shell is
divided into sub energy shells. Each sub shell corresponds to several electron cloud space. The
energy of the subshells increases as the value of increases. Azimuthal quantum number has
integral values ranging from = 0, 1 2, 3 to n-1. The subshells are designated as s, p, d, f and so
on. The subshells all have different energies. The energy of the subshells are in this order
s<p<d<f.

Table 3.1Summary of subshells, number of orbitals, shape of orbitals and their maximum
number of electrons

Subshell Number of Orbitals Shape of Orbitals Maximum No. of Electrons

S 1 Spherical 2
P 3 Dumbbell 6
D 5 Double Dumbbell 10
F 7 Complex 14

Figure 3.2: Shape of Orbitals

(a) The one s-orbitals

(b) The three p-orbitals

29
 (c) The five d-orbitals

Magnetic Quantum Number (m): Magnetic Quantum Number (m):This specifies the
permitted orientation in space for an electron cloud. It gives the number of orbital types in an
energy level. And it has integral values of m = - --- 0 --- + . That is, the number of orbital in a
sub shell is given by 2 + l.

When = 0, m = 0, which means that there is only one orientation, which is a spherical
distribution (s-sub level or s-orbital).When = I, then m = -l, 0, + 1, that is there are three
permitted orientation. The axes of these dumb-bells shaped orbital lie at 90° to each other. They
are designated as Px, Py and Pz as shown in Fig. 3.2b, corresponding to major charge
concentration along each of the three Cartesian coordinates.
Table 3.2: Relationship between Quantum Numbers and Atomic orbital

Principal Subsidiary Number of Number of Atomic Number of

Quantum No. Quantum No. Sublevels Orbital Orbital Electron
(n) (n) m=2 +1
1 0 1 1 1s 2
0 1 2s
2 2 8
1 3 2p
0 1 3s
3 1 3 3 3p 18
2 5 3d
0 1 4s
1 3 4p
4 4 32
2 5 4d
3 7 4f

Table 3.2 shows the first four energy levels in the quantum mechanical model of the atom.
Spin quantum number(s): This does not arise from Schrodinger equation but comes from other
consideration. It gives the direction of electron spin on its axis. It has two values: + and - .
This means that an electron in a particular orbital has two permitted orientation of spin on its
own axis, opposite to one another s = + (for electron spinning in clockwise direction) and s = -
(for anticlockwise direction).

30
All the orbitals in a particular sub-shell are of equal energy. As seen in Figure 5.3. The energy
gap between successive shells gets smaller as the principal quantum number increases. This
explains why the 3d orbital which is an orbital in an inner shell is at a higher energy level than
the 4s orbital in the next shell further away from the nucleus but lower than the 4p orbitals.
Example 3.1: How many orbitals do we have in the second principal level n = 2?
Solution: The second principal energy level has 2 sub-shells: 2s and 2p orbitals. The 2s sub-shell
has one orbital, and the 2p sub-shell has 3 orbita1‟s so in all, we have four orbitals in the second
principal level.
Can you write the number of orbitals in:
(i) The fourth energy level n = 4
(ii) The 4s orbital
3.3 ELECTRONIC CONFIGURATION OF ELEMENTS
Electron configuration of an element is the arrangement of electrons in its atomic orbital when it
is at the ground state. In order to understand how electrons are arranged in orbitals. It is
necessary to understand some basic principles. These principles are discussed below;

3.3.1 HEISENBERG UNCERTAINTY PRINCIPLE

This principle states that it is impossible to know simultaneously at the same time the exact
position and momentum of small particles like electrons.
3.3.2 PAULI’S EXCLUSION PRINCIPLE
This principle states that in an atom of many electrons, no two electrons in that atom can behave
identically or have the same set of all the four quantum numbers. That is, even if the principal
quantum number, subsidiary quantum number and the magnetic quantum number, are identical.
The spin quantum number must have opposite spin on its axis. That is the spin must be clockwise
and anticlockwise.
This is used to represent an electron and its direction of spin
While an orbital containing an electron pair is represented as

3.3.3 HUND’S RULE

This states that electrons will singly occupy orbitals of equal energy (degenerate orbitals) until
all the orbitals contain one electron each with parallel spins before pairing with opposite spin.

1s 2s 2px 2py 2pz

3.3.4 AUFBAU’S PRINCIPLE OR BUILDING - UP PRINCIPLE

The Aufbau‟s principle is:
1. Electrons go into orbital with the lowest energy before occupying higher energy level.

31
 2. The Pauli‟s exclusion principle (two versions).
(a) It is impossible for two electrons in the same orbital to have the same or identical spin
quantum number.
(b) An orbital can contain a maximum of two electrons.
3. Electrons will fill a set of degenerate orbital singly with parallel spin before pairing with
opposite spin.
Finally, electron structures are shown by writing down the list of orbitals, with number of
electrons in each orbital shown as a superscript e.g. the 9 electrons in a fluorine atom can be
arranged in the order 1s2 2s2 2p5. This order is referred to as electronic configuration of F.
By following the arrows in figure 3.4 below, it will help you work out the correct order of
orbitals in the electron structures and thus write the electronic configuration of elements once
you know the atomic number

Figure 3.4: Order of orbitals in the electron structures.

Table 3.3: The electronic configuration of the first 10 elements of the periodic table

Atomic Element Electronic configuration

1 H 1s1

2 He 1s2

3 Li 1s2 2s1

4 Be 1s2 2s2

5 B 1s2 2s2 2p1

32
 6 C 1s2 2s2 2p2

7 N 1s2 2s2 2p3

8 O 1s2 2s2 2p4

9 F 1s2 2s2 2p5

10 Ne 1s2 2s2 2p6

From the table above, Helium and Neon both have their outermost s orbital and p orbital filled.
This makes them very stable and they are referred to as noble gases. The next element sodium
begins the filling of the next energy level n = 3.
The electronic configuration of Neon 1s2 2s22p6can also be represented in a box diagram as:
1s 2s 2p

In Neon all the orbitals are filled.

Sodium has atomic number of 11, so the electronic configuration is written as ls2 2s3 2p6 3s1 The
3s orbital has one unpaired electron.
Magnesium has atomic number of 12, its electronic configuration is written as ls2 2s2 2p6 3s2
Aluminum has atomic number of 13, its electronic configuration is written as ls2 2s2 2p6 3s2 3p1
Silicon is the next with atomic number of 14, its electronic configuration is written as ls 2 2s2 2p6
3s23p2
One electron is added to the 3p orbitals as atomic number of the elements increases until the 3p
orbitals of Argon with atomic number 18 is completely filled. The next element is potassium, the
electrons do not enter the 3d orbital instead it goes into the 4s orbital because the energy of the
3d orbital is slightly higher than that of the 4s orbital but lower than the 4p orbital. It then
follows that the 4s orbital has to be completely filled before the 3d orbitals are filled. It then
follows that the electronic configuration of K is written as 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Perfectly half-filled or completely filled orbitals confer stability on atoms. Since atoms strive
towards stability, an atom like Cr would prefer to have a half filled 3d orbital and the electronic
configuration which is supposed to be 1s2 2s2 2p6 3s2 3p6 4s2 3d4 then becomes 1s2 2s2 2p6 3s2 3p6
4s1 3d5

3.5 HYBRIDIZATION OF ATOMIC ORBITAL

Some atoms form covalent bonds that are different from what their electronic configuration

33
suggests. When these bonds are formed between atoms, there is a change in the nature of the
Atomic Orbitals in each atom. This peculiar bonding character can be explained with the concept
called hybridization. It involves combining a number of orbitals to create a set of an equal
number of new orbitals, where each of the new hybrid orbitals has properties which are an
average of those of the orbitals from which they were created.
Thus, hybridization is a process whereby the orbitals of an atom (usually a central atom) interact
to get a set of equivalent orbital called the HYBRID ORBITAL. Hybridization can also be
defined as the mixing or overlapping of orbital of an atom to give a set of equivalent orbitals
known as hybrid orbital. The hybrid orbital shows characteristics of both atomic orbitals.
A number of different types of hybrid orbitals are known for elements. These hybrid orbitals and
the shape of the resulting molecules are given in table 3.4 below. However, only a few of the
hybrid orbitals will be discussed here.
Table 3.4: hybrid orbitals types in coordination compounds

Atomic Orbitals Hybrid Type Numbers of Structure

Orbitals
Sp sp 2 Linear
Sd sd 2 Linear
spp sp2 3 Trigonal planar
sppp sp3 4 Tetrahedral
dspp dsp2 4 Square planar
dsppp dsp3 5 Trigonal bipyramid
sppdd sp2d2 5 Square-base bipyramid
ddsppp d2sp3 6 Octahedral
spppdd sp3d2 6 Octahedral

3.5.1 sp-HYBRIDISATION
In considering the shape of a hybridized orbital, the electronic configuration of the central atom
must be known. Let‟s consider BeCl2; the central atom is Be, and its ground state electronic
configuration is;
Be = 1s2 2s2
Beryllium has to be excited to generate orbitals to accommodate the two chlorine atoms. Thus if
energy is supplied to raise one of the 2s electrons to a higher energy level the excited state
electronic configuration of Be will be;
Be* = 1s2 2s1 2p1
More specifically, the electronic configuration of the excited beryllium atom can be written as;

Be* =
1s2 2s1 2px1 2py 2pz

34
And the excited state valence shell electronic configuration is;
Be* =
2s1 2px1 2py 2pz
The two chlorine atoms will be accommodated in the 2s and 2px orbitals created as a result of
the excitation. One would expect that one chlorine atom would occupy the 2s1 orbital while the
other would occupy 2px1 orbital, making two non-equivalent BeCl2 hybrids. However, the two
BeCl2 bonds formed are identical in every respect, indicating that the 2s and 2p orbitals mixed
(hybridized) to form two equivalent sp hybrids orbital.
Also, because one s and one p orbital are used in the hybridization, the shape of the molecule
will be a linear geometry.

3.5.2 sp2-HYBRIDISATION
For this, we are going to consider boron trifloride (BF3). Here the central atom is boron (B) and
its ground state (i.e. the lowest energy state) electronic configuration of boron is;
B = 1s2 2s2 2p1
Boron has to be excited to generate orbitals to accommodate all the three fluorine atoms. Thus if
energy is supplied to raise one of the 2s electrons to a higher energy level the excited state
electronic configuration of Be will be;
B*=1s2 2s1 2p2
But more specifically, the electronic configuration of the excited beryllium atom can be written
as;

B* =
1s2 2s1 2px1 2py 2pz
And the excited state valence shell electronic configuration is:

B* =
2s1 2px1 2py 2pz
The three fluorine atoms will be accommodated in the 2s1, 2px1 and 2py1 orbital created as a
result of the excitation. One would expected three non- equivalent BF3 hybrids. However, the

35
three BF3 bonds formed are identical in every respect, indicating that the 2s, 2px and 2py orbitals
mixed (hybridized) to form three equivalent sp2 hybrids orbital.
Also, because one s and two p (sp2) orbitals were used in the hybridization the shape of the
molecule will be a triangular planar. The three sp2 orbitals lie in a plane with an angle 120°
between any two.

3.5.3 Sp3-HYBRIDISATION
Here, we will be considering methane (CH4). The central atom is carbon (C) and its ground state
(i.e. the lowest energy state) electronic configuration is:
C = 1s2 2s2 2p2
Carbon has to be excited to generate orbitals to accommodate the four hydrogen atoms. Thus if
energy is supplied to raise one of the 2s electrons and one of the 2p electrons to a higher energy
level,the excited state electronic configuration of C will be;
C* = 1s2 2s1 2p3

But more specifically, the electronic configuration of the excited carbon atom can be written as;

C* =
1s2 2s1 2px1 2py 2pz
And the excited state valence shell electronic configuration is;

C* =
2s1 2px1 2py 2pz
The four hydrogen atoms will be accommodated in the 2s1, 2px1, 2py1 and 2pz orbitals created as
a result of the excitation. Four CH4 bonds are formed which are identical in every respect,
indicating that the 2s, 2px, 2py and 2pz orbitals mixed (hybridized) to form the four equivalent
sp3 hybrids orbital.
Also, because one s and three p (sp3) orbitals were used in the hybridization, the shape of the
molecule will be a tetrahedral. All the hydrogen carbon hydrogen angles are 109.5°

36
It is interesting to note that hybrid formed by only using the s and the p (i.e. sp1, sp2 and sp3)
orbitals in molecule complies with the octet rule. This is because regardless of the type of
hybridization in an atom involving one s and three p orbitals will be four orbitals which is
enough to accommodate a total of eight electrons in a compound. However the octet rule does
not hold in some molecules where the atom may use the d orbital in addition to the s and p
orbitals to form hybrid orbitals.
3.5.4: s, p and d ORBITALS-HYBRIDISATION
Atoms of elements in the second period of the periodic accommodate a maximum of eight
electrons in their valence shell and also the s and p orbitals for their hybrid. This explains why
they usually obey the octet rule. However, elements of the third period on, with more than eight
electrons in their valence shell cannot always form hybrid molecules by using only the s and p
orbitals. That is the formation of these hybrids must include the d orbitals.
As an illustration, PF5 will be considered. Here the central atom is phosphorus (P) and the ground
state (i.e. the lowest energy state) electronic configuration of phosphorus is;
P = 1s2 2s2 2p6 3s2 3p3
Phosphorus has to be excited to generate orbitals to accommodate all the five chlorine atoms.
Thus if energy is supplied to raise one of the 3s /3p electrons to a higher energy level the excited
state electronic configuration of P will be:
P* = 1s2 2s2 2p6 3s1 3p3 3d1
But more specifically, the excited state valence shell electronic configuration is;

P* =
3s1 3px1 3py1 3pz1 3d 3d 3d 3d 3d
The five fluorine atoms will be accommodated in the 3s, 3px, 3py, 3pz and 3d orbitals created as
a result of the excitation. Also, because one s, three p and one d (sp3d) orbitals were used in the
hybridization, the shape of the molecule will be a trigonal bipyramid.

Here, there are ten electrons around the phosphorus atom, which means that the octet rule has
been exceeded. Thus the use of the d orbital in addition to the s and p orbitals to form covalent
bonds is an example of valence - shell expansion (expansion to the octet rule).

37
As another illustration, let‟s consider SF6. Here the central atom is sulphur (S) and the ground
state (i.e. the lowest energy state) electronic configuration of sulphur is;
S = 1s2 2s2 2p6 3s2 3p4
Sulphur has to be excited to generate orbitals to accommodate all the six fluorine atoms. Thus if
energy is supplied to raise one of the electrons to a higher energy level the excited state
electronic configuration of S will be:
S* = 1s2 2s2 2p6 3s1 3p3 3d2
But more specifically, the excited state valence shell electronic configuration is;

S* =
3s1 3px1 3py1 3pz1 3dz2 3dx2 – y2 3dxy 3dyz 3dxy
The six fluorine atoms will be accommodated in the 3s, 3px, 3py, 3pz, 3dz 2 and 3dx2 – y2
orbitals created as a result of the excitation. Also, because one s, three p and two d (sp3d2)
orbitals were used in the hybridization, the shape of the molecule will be an octahedral. Here
also, there are twelve electrons around the sulphur atom; which means that the octet rule has also
been exceeded. Thus the use of the d orbital in addition to the s and p orbitals to form covalent
bonds is an example of valence – shell expansion (expansion to the octet rule).

38
PRACTICE QUESTIONS
1. (a) How many orbitals are in the following:
(i) The 3p orbitals
(ii) The 2s orbitals
(iii) The third energy level corresponding to n = 3.
(b) Write the maximum number of electrons that each orbital and each energy level can
take.
2. Give reasons for the following:
(i) Electrons will fill the 4s orbital before other electrons will fill in the 3d orbitals.
(ii) An unpaired electron will enter into an} of the vacant 3p orbital during the filling of
orbitals
(iii) No two (2) electrons have the same four quantum numbers.
3. Write the electronic configuration of the following elements K, S, P, and Ar
4. Deduce the shape of the following molecules.
(a) PCI5 (b) PF3 (c) SP6 (d) XeF4 (e) CH4 (f) NH3
(Xe = 54, S = 16, P = 15, C = 6, N = 7, Al = 13, B = 5, Be = 4)

39
 CHAPTER 4
4.0 CHEMICAL SYMBOLS, FORMULAS AND EQUATIONS

4.1 CHEMICALSYMBOLS: Chemical symbols are the chemist abbreviated form of writing or
representing the names of elements. The principle applied when representing element was put
forward by Berzkelius in 1814. The principle entails the following.

1. The first principle uses the first letter, (written in capital letter) of the name of an element
as its symbol. Examples includes; Hydrogen (H), Boron (B), Carbon (C), Nitrogen
(N) Oxygen(O) Fluorine (F)Phosphorus (P)

2. When the first letter had already been adopted. The first letter and any other letter in the
name of the element is used as the symbol. Here, the first letter is written in capital letter
while the second letter is written in small letter. Examples includes ; Helium (He),
Lithium (Li) Beryllium (Be), Neon (Ne), Magnesium (Mg), Aluminium (Al)

3. When these two methods have been adopted, the symbol of the elements is then derived
from the Latin names of the elements using method one and two above. Example
includes; Sodium (Natrium, Na), Potassium (kalium, K), Iron ( Ferrum, Fe) and
Copper (Caprum, Cu).

As earlier stated, these abbreviations s are written in capital letter when the symbol is only one
letter. In cases where it has two letters, only the first letter is written in capital letter, while the
other letter is written in small letter.

The symbols of an element represent

1. One atom of the element

2. A definite mass of the element often expressed in grams

4.2 CHEMICAL FORMULA

A chemical formula is an expression involving chemical symbols and numerical. The symbols
represents the different types of elements present (i.e. composition) in the compound while the
numerical indicates the number of atoms in one molecule of a compound, when it is written as a
subscript after the symbol of the element. Example is H2 which show that it contains two atoms
of hydrogen; H2SO4 shows that the chemical formula contains two atoms of hydrogen, one atom
of sulphur and four atoms of oxygen.

There are basically three types of chemical formulas namely empirical, molecular and structural
formulas.

40
 i. EMPIRICAL FORMULA: This is the simplest formula of a compound
that shows the simplest whole number ratio of atoms of different elements
present in a compound. Hence the empirical formula of the compound
C2H4O2 is CH2O, where the integer multiplier is 2.

Normally, the results of chemical analysis are expressed as percentage by mass of each
constituent element, so to know the identity of the compound the empirical formula will be
calculated from the percentage composition. Calculation of the empirical formular of the
compound entails first determining the relative number of moles of atoms of each
elementpresent in the given mass of the compound. Thereafter, the number of moles of each
element is then divided by the smallest number of the mole present.

4.2.2 MOLECULAR FORMULA: This is a formula of a compound that shows the exact
(actual) number of atoms of different element present in a compound. The molecular formula is
given by

Molecular Formula = Empirical formula X integer multiplier

Molecular formula = n (Empirical formula)

Sometimes, empirical formula and molecular formula can be the same. This is when the
molecular formula cannot be reduced further. Examples includes NH3 (ammonia), CaCO3
(calcium trioxocarbonate (IV), H2O (water) CO2 (carbon(IV)oxide) etc.

4.2.3 STRUCTURAL FORMULA: - The structural formula shows the way that atoms are
joined together in a molecule. Knowledge of the structural formula of compound is important in
the study of chemistry because some compounds may have the same molecular formula and
empirical formula and the only thing that will show that the compounds are different is their
structural formula. As an illustration, Butanol and ethyl ether have the same empirical and
molecular formula as C4H10O. The only thing that differentiates the two and gives both their
respective unique set of properties is the structural formula.
H H H H H H H H

H C C C C OH H C C O C C H

H H H H H H H H

Butanol Ethylether

Example 4.1

Find the empirical formula of a compound which contains 80% carbon and 20% hydrogen by
mass.

41
(Relative atomic masses, C = 12, H = 1)

Solution

Step 1: Divide the percentage by mass of each element by the relative atomic mass of the
element

For carbon -

For Hydrogen -

Step 2: Divide through by the smallest number since atoms cannot be in fraction

, 20
Therefore empirical formula is CH3

Example 4.2

An organic compound contains 72% carbon, 12% hydrogen and 16% oxygen by mass. Calculate
the empirical formula of the compound (Relatives atomic masses; H = 1, 0 = 16, C= 12)

Solution

Step1

C= O= H=
Step2: Dividing through by the smallest number

: - Empirical formula = C6H12O

Example 4.3: A pure compound contains 40% carbon, 6.7% hydrogen and 53.3% oxygen. Find

(i) The empirical formula

(ii) The molecular formula if a mole weighs 60g (Relative atomic masses; H = 1, C = 12, O =
16)

Solution

42
Dividing through by the smallest we get

:- Empirical formula is CH2O

(ii) Molecular formula = n (empirical formula) - - - - - - - - (1)

I mole of molecular formula = n (mole of empirical formula

I mole empirical formula = 12gC + 2gH + 16gO

= 30g

From question, 1 mole molecular formula = 60g

From equation (1)

60 = n (30)

60 = 30n

: - Molecular formula = 2(empirical formula)

= 2(CH2O)

= C2H4O2

4.3 PREDICTING FORMULAS FROM VALENCIES

Recall that in chapter one we defined vacancy as the number of electrons an atom can lose, gain
or share to acquire an octet or duplet electronic configuration. The formulas of compounds can
be deduced from the valences of component elements or radicals using the following rules

Rule 1: Write the symbols of the component elements or radicals

Rule 2: Place the valences of each elements or radical below the respective element or radical

Rule 3: Interchange the valences and write them as subscript immediately after the respective
symbols of the atoms.

Rule 4: Write the formula of the compound by first writing the metals followed by the non-
metals.

43
Note: When the subscript is one, it is disregarded and when all the subscripts can divide
through, they are further reduced.

Examples 4.4

Write the formula of the compound formed when iron (III) reacts with oxygen.

Rule 1: Fe O

Rule 2: Fe O

3 2

Rule3: Fe O

3 2
Rule 4: Fe2O3

Example 4.5

What is the formula of aluminum sulphide

Rule 1: Al S

Rule 2: Al S

3 2

Rule3: Al S

3 2
Rule4: Al2S3

Example 4.6
Write the formula of sodium oxide
Rule 1: Na O

Rule 2: Na O
1 2

Rule 3: Na O

1 2
Rule 4: Na2O
44
These rules are the same even when writing the formulas of compounds involving radicals.
Radicals are groups of atoms collectively carrying a single charge. The only modification is that
the radical is enclosed in a bracket if it has a value above one. Below in table 4.1 are some
radicals and their valences.

Table 4.1Examples of some radicals and their valencies

Radical Formula Valency
Ammonium NH4+ 1
Hydroxide OH- 1
Trioxonitrate (V) NO3- 1
Trioxocarbonate(IV) CO32- 2
Tetraoxosulphate (VI SO42- 2
Tetraoxophosphate (V) PO43- 3

Example: 4. 7
Write the formula of calcium sulphate

Rule 1: Ca SO4

Rule 2: Ca SO4

2 2

Rule 3: Ca SO4

2 2

Rule 4: Ca2(SO4)2.

Since both subscripts can divide through they can be further reduced, leaning our formula as
CaSO4

Example 4.8

Write the formula of sodium trioxocarbonate(IV)

Rule 1: Na CO3

Rule 2: Na CO3

1 2

Rule 3: Na CO3

1 2
Rule 4: Na2CO3

45
In summary, a chemical formula shows how many atoms of each element present in a
compound. When a group of atoms is put in a bracket e.g. Al2(CO3)3, the subscript that follows
the bracket applies to all the atoms inside the bracket only. As an illustration, the formula of
aluminum trioxocarbonate(V) implies that for each formula unit of aluminum troxocarbonate(V)

(1) There are two aluminum ions

(2) There are 3 trioxocarbonate ions

(3) In each trioxocarbonate ion there is one carbon atom and three oxygen atoms.

Al2 (CO3)3

2 aluminim ion 3 trioxo carbonate ion

4.4. CHEMICAL EQUATIONS

A chemical equitation is a compressed statement about a chemical reaction, using symbols and
formulas. A reaction can be written in words for example oxygen reacting with hydrogen to
produce water
Oxygen + Hydrogen water.

This type of equation is of little importance to the chemist as it does not indicate the quantities of
each reactant taking part in the reaction and the quantities of the product formed in cause of the
chemical reaction. It does not even specify the state of the reactant and product.

For a chemical equation to be useful to chemist, the actual quantities of the reactants and
products must be specified. This is where the law of conservation of matter comes into place.
According to the law, the total quantity of the reactant must equal to the total quantity of the
product formed. A chemical equation that has this quality is said to be a balanced chemical
equation.

4.5. BALANCING CHEMICAL EQUATIONS

A balanced chemical equation is an exact symbolized expression of a chemical reaction, where

all the atoms of the different elements in the reactants are equal to all the atoms of different
elements in the products.

In balancing a chemical equation, the following steps should be taken:

Step 1: Write a word equation for the reaction.

Step 2: Write the correct formula of all the reactants and products

Step 3: Select coefficients that will make the equation balanced Note, do not change the
subscript in the formulas of the compound while balancing

46
Example 4.10

Write a balanced chemical equation for the reaction between chlorine and sodium bromide to
produce sodium chroride and bromine

Solution

Step 1:

Chlorine + sodium bromide sodium chloride + Bromine

Step 2:

Determine the formulas of sodium bromide and sodium chloride using methods for predicting
formulas, discussed earlier

Cl2 + NaBr NaCl + Br2

Step 3: Coefficient are selected in order to balance the equation. The subscript must not be
changed. Coefficients are whole numbers written before the formula of a compound, element,
ion, molecule, indicating the relative number of unit reacting in the chemical reaction.

Cl2 + 2NaBr 2NaCl + Br2.

Example 3.11

Write a balanced chemical equation for the reaction between hydrochloric acid and calcium
trioxocarbonate (IV) to produce calcium chloride, water and carbon(IV) oxide

Solution

Step 1:

Hydrochloric acid + calcium trioxocarbonate (IV) Calcium chloride + water +

carbon(IV)oxide

Step 2:

Using the steps for predicting formulas, predict the formulas for calcium trioxocarbonate(IV),
calcium chloride, carbon(iv)oxide, hydrochloric acid, and water.

HCl + CaCO3 CaCl2 + H2O + CO2

Step 3: Select coefficient on either sides of equation‟s formulas that will balance the equation.

2HCl + CaCO3 CaCl2 + H2O + CO2

Example 4.12

47
Write the balanced equation for the reaction between aluminum sulphate and calcium chloride to
produce aluminum chloride and a white precipitate of calcium sulphate solution.

Step 1:

Aluminium sulphate + calcium chloride Aluminum chloride + calcium sulphate

Step 2:

Al2 (SO4)3 + CaCl2 AlCl3 + CaSO4

Step 3:

Al2 (SO4)3 + 3CaCl2 2AlCl3 + 3CaSO4

N.B
The oxidation states of elements or radicals with variable oxidation state are always
stated e.g. carbon (II) oxide implies that the carbon has the oxidation state of + 2. Iron
(III) implies oxidation state of +3.

48
 CHAPTER 5
5.0 STOICHIOMETRY

This is the aspect of chemistry that deals with quantities of substances. These quantities can be
expressed in terms of number of moles, mass, volume and Avogadro‟s number. And these are
based on;

i. Conservation of mass
ii. Relative masses of atoms
iii. The mole concept

This concept is used in all areas of chemistry which include;

i. predicting the quantities of reactants and products

ii. interpreting analytical results in chemistry
iii. preparation of standard solutions
iv. ascertaining the cost effectiveness of large scale chemical reactions

5.1 THE MOLE CONCEPT

The mole concept is the expression of quantities (i.e. amount of solute in solution or solvent) in
terms of number of moles, mass, volume and Avogadro‟s number.

5.1.1 THE MOLE AND THE ADVOGADRO’S NUMBER

The mole is the chemist way of measuring the amount of a substance. One mole of a chemical
species contains exactly one gram atomic mass, molecular mass or formula mass of the species.
For example:

1 mole = One atomic mass

Fluorine = 19g

Calcium = 40g

A mole of specie also contains a constant number of the elemental particles, atoms, ions
molecules etc. The number is 6.02 x 1023 and it is called the Avogadro‟s number. One mole
ofspecie will contain one atomic mass of that specie and will also contain the Avogadro‟s number
of particles.

49
Table 5.1 Relationship between atomic mass and the Avogadro’s number

ONE MOLE ONE ATOMIC ONE AVOGADROS

MASS NUMBER

Hydrogen 1g 6.02 x 1023 atoms

Boron 11g 6.02 x 1023 atoms

Fluorine 19g 6.02 x 1023 atoms

There is a relationship between one mole, one gram atomic mass (gram atomic weight) and the
number of particles (Avogadro‟s number) of a chemical species. Their values are inter -
changeable. It is also important to note that when one is converting from any of these three
quantities to another, one mole, one atomic mass and one Avogadro number is used as the
conversion factor.

Example 5.1
Express as mole (a) 24g of carbon (b) 10g of Neon (c) 120g of calcium

Solution

Since we are expected to convert from mass to mole, then our conversion factor will be 1 mole =
1 gram atomic mass

(a)
1 mole = 12g
x mole = 24
Note that like terms are always on the same side of the equation. Cross multiply and make
x subject
24g x 1 mole = 12g X xmole
24g x 1 mole
 x mole  2 moles
12g
: - 24g of carbon is 2 moles

(b) 1 mole of Neon = 20g

x mole of Neon = 10g

10 g x 1 mol
x mol   0 .5
20
:- 10g of Neon is 0.5 mol
(c) 1 mole of calcium = 40g

50
 X mole of calcium = 12g
120g x 1 mol
x mol  3
40

12g of calcium is 3 moles

Example 5.2
What is the mass of 0.3mol of phosphorus and how many atoms does it have?

Solution
For the first part of the question, we are expected to covert from mole to mass. Therefore,
our conversion factor is:
1 mole = 1 gram atomic mass

1 mole phosphorus = 31g

0.3 mole phosphorus = x g

Note that like terms are always on the same side of the equation. Cross multiply and
make x subject

1 mole x xg = 31g x 0.3mol

31g x 0.3mol
xg   9.3g
1 mol
: - 0.3mol of phosphorus has mass of 9.3g.

In the second part of the question, you are expected to calculate the number of
atoms (Avogadro's number) in 0.3moles or 9.3 gram phosphorus. Depending on how we
want to solve this problem, ourconversion factor can either be

i) 1 mole = 1 Avogadro number (6.02 x 1023) OR

ii) 1 gram atomic mass = 1 Avogadro number (6.02 x 1023)

But whichever path we take, we will still arrive at the same answer.
Solving from the first path, we have,
1 mol = 6.02 x 1023
0.3mol = x
xx 1mol = 0.3mol x 6.02 x 1023

0.3mol x 6.02 x1023

x
1mol
x= 1.806 X 1023 atoms in 0.3mole phosphorus

Try and solve the question, using the second path way.

51
5.1.2 THE MOLE AND THE GRAM FORMULA MASS
The gram formula mass is the quantity of a chemical specie whose mass in gram is
numerically equal to the sum of all the atomic masses of its constituent elements. When the
formula is for an element, e.g. B, F, O, Zn, N, etc we use the atomic mass. Also when the
formula is that of a molecule (e.g. H2O, CH4, CaCO3etc.) the term gram molecular mass is
used in place of gram formula mass. The term gram formula mass is still retained for ionic
compounds since it also represent a mole and one Avogadro number.

Example 5.3
Determine the gram formula mass of CaCO3

Solution
The atomic masses of the constituent elements are
Element Gram Atomic mass
Ca 40
C 12
O (16 x 3) = 48
Gram molecular mass = 40+12+48=100g

The gram atomic mass of oxygen is multiplied by three because there are three atoms of
oxygen in the compound's formula. Therefore, the sum in gram of the masses of all the
atoms in the formula CaCO3 is 100g.

This, implies that one mole of CaCO3 is equivalent to 100g and has 6.02 x 1023 number of
CaCO3 molecules.

5.1.3 MOLE, MASS AND VOLUME RELATIONSHIP

At standard temperature, (0OC or 273k) and standard pressure (760mmHg or 101.3 x 103
pa), the volume occupied by one mole of any gas is a constant value. That value is called
the molar volume and it is numerically equal to 22.4dm 3• For example, the gram molecule
mass of one mole of carbondioxide (CO2) is

Element Gram Atomic Mass

C 12
O 16 x 2 = 32
449
This one mole, contains 6.02 x 10 molecules and occupies a volume of 22.4dm3 at stp
23

In summary,
1 mole = one gram formula mass
1 mole = 6.02 x 1023 atoms, molecules, formulas, species etc.
1 mole = 22.4dm3 for any gas at s.t.p

Examples 5.4
Calculate the (a) volume at s.t.p of ammonia in 8.50g of ammonia gas.
(b) How many molecules of ammonia will there be in the sample

52
(c) Express the volume at s.t.p in moles (one gram atomic mass of NH 3 = 17g, one
Avogadro number = 6.02 x 1023)
Solution

(a) 17g = 22.4 dm3 (conversion factor) 8.59 = x

8.5 gx22.4dm3
x=  11.2dm3
17 g

(b) 179 = 6.02 x 1023 molecules (conversion factor)

8.5g = x

8.5 gx6.02 x 10 23
X= 
17 g

(c) 1 mole = 22.4dm3 (conversion factor)

x = 11.2dm3

11.2dm3 x 1 mole
x=  0.5mile
22.4dm3

5.1.4. MOLE RATIO, MASS AND VOLUME RELATIONSHIP IN CHEMICAL

EQUATION

The whole number in front of the reactant and product formula in a chemical reaction represents
the number of moles of reactants, reacting to give the number of moles of product. These whole
numbers are the mole ratio of the reactants and products in a chemical reaction. When no whole
number is written in front of a formula in a chemical equation, it implies that the mole ratio is
one. Example

Equation 2H2+ O2 2H2O

Mole ratio 2 1 2

Reacting mass (2x2) (16x2) (18x2)

Reacting mass 4g 32g 36g

From the above example, it is clear that the mass that reacted is simply the product of the number
of moles and the gram formula mass.

: - Reacting mass = Number of moles x gram formula mass Rearranging, we get

53
 Re acting mass gram
Number of moles =
Gram formula mass

Example 5.5

A sample of CO2 has a mass of 11.0 grams

(a) Calculate the number of moles of CO2 in the sample

(b) What volume will the sample occupy at s.t.p. (C = 12 0 =16)

Solution
(a) Reacting mass= 11.0g
Formula mass= 44g
No. of mole = x

Reacting mass = formula mass x number of moles

Re acting mass
numberof moles 
formulamass
11.0 g
 0.25mol
44g
(b) At Stp 1 mole = 22.4dm3
0.25mole = x dm3

0.25mol x 22.4dm3
X=  5.6dm3
1

Example 5.6
Calculate the mass of carbon (iv) oxide CO2 produced on burning a mass of 104g ethyne
C2H2 (C=12, O=16, H=l)

Solution
2C2H2 + 5O2 4CO2 + 2H2O
Mole ratio 2 5 4 2

Gram formula 2 x 26, 32 x 5, 44 x 4 18 x 2

Mass 52g 160g 176g 36g

From the equation, 176g of CO2 is produced on burning 52g of C2H2. What mass of CO2 will be
produced on burning 104g of C2H2?

As usual, arrange like terms on the same side of the two equations, cross multiply and make the
unknown the subject

52g C2H2 produced 176g of CO2

54
 104g C2H2 producedxg of CO2

104 x 176
x  352
52

Example 5.7
What mass of zinc tetraoxosulphate (VI) is obtained from reacting 10g of zinc with excess
dilute tetraoxosulphate (VI) acid. (Zn = 65, S =32, O=16)
Zn + H2SO4 ZnSO4 + H2

Solution
Question summary
What mass of ZnSO4 is obtained from 10g of Zn?
From the equation, the conversion factor is 161g ZnSO 4 is obtained from 65g Zn
i.e. 161gZnSO4 = 65g Zn
X gZnSO4 = 10g Zn

X=

5.2.STIOCHIOMETRIC CALCULATIONS INVOLVING A LIMITING REAGENT

So far, we have been dealing with reaction were reactants are mixed in stoichiometric
quantities. That is reactants reacts at exactly the correct amount and are completely used up
in the reaction.

There are some other instances where some reactants are not enough to completely react
with the others, or when one reactant is in excess of what would exactly and completely react
with the other reactant. In this case, the insufficient reactant will be consumed before the
reactants in excess are used up. And as such the quantity of the product is determined by the
insufficient reagent, which when used up no more products can be formed. The insufficient
reagents limit the amount of the product that can be formed and therefore called the limiting
reactant or reagent.

Example 5.8
What mass of zinc is required to completely react with 73.9g of tetraoxosulphate (VI) acid?
(Zn = 65, S =32, O=16)
Zn + H2SO4 ZnSO4 + H2

Solution
Question summary
The question is asking what quantity of zinc will completely use up 73.9g of
tetraoxosulphate (VI) acid.

From the equation, one mole of zinc will react completely with one mole of

55
tetraoxosulphate (VI) acid and we were giving the reacting mass of H 2SO4. We can then
use this value to calculate the number of mole of H 2SO4 that reacted.

Reacting mass (H2SO4) = molecular mass x number of moles

Therefore,

Number of moles of H2SO4 =

Recall from the equation that one mole of zinc will completely react with one mole of H2SO4.
Therefore since the number of moles of H 2SO4 that reacted is 0.754mol, then it will react
with 0.754mol of Zn.

Now to get the mass of zinc that reacted we use the same formula

Reacting mass (Zn) = molecular mass x number of moles

Reacting mass (Zn) = 65g/mol x 0.754 moles

Reacting mass (Zn) = 49.01g

This question can also be solved using a direct and quick method thus;

Zn + H2SO4 ZnSO4+ H2
Mole ratio: 11 1 1
Gram formula: 1 x 65, 1 x 98 1x 161 1 x 2

Mass: 65g 98g 161g 2g

From the equation, 1mol of Zn react with 1mol of H2SO4

i.e. 65g Zn98g H2SO4

Xg 73.9g
Cross multiply and make Xg subject
Xg =

The result obtained from the last example tells us that 49.01g of zinc mixed completely
with 73.9g of H2SO4.However, if any of this reactant is reduced for example Zn to
35.0g, it will limit the amount of product that will be formed. In any stoichiometric
problem, it is also important to determine which reactant is limiting in order to
accurately determine the amount of product that will be formed.

Example 5.9
What mass of zinc tetraoxosulphate (VI) can be produced when 35.0g of zinc is allowed

56
tocompletely react with 73.9g of tetraoxosulphate (VI) acid? (Zn = 65, S =32, O=16)

Zn + H2SO4 ZnSO4 + H2

Solution
Question summary
The question is asking what quantity of zinctetraoxosulphate (VI) will be produced by
completely reacting 35.0g zinc with 73.9g of tetraoxosulphate (VI) acid.

From the equation, one mole of zinc will react completely with one mole of
tetraoxosulphate (VI) acid and we were giving the reacting mass of both Zn and H2SO4. We
can then use these values to calculate the number of mole of the reactants.

Number of moles of H2SO4 =

Number of moles of Zn=

From the equation one mole of each reactant will completely react with the other. It becomes
obvious that zinc is the limiting reagent. Also, since one mole of zinc will produce one mole of
zinc tetraoxosulphate (VI), than the mole of zinc should be used to calculate quantity of
zinctetraoxosulphate (VI) that will be produced.

Mass (ZnSO4) = molecular mass x number of moles

Mass (ZnSO4) = 98g/mol x 0.54 moles

Mass (ZnSO4) = 52.78g

5.3OTHER METHODS OF EXPRESSING CONCENTRATION OF SOLUTIONS

There are other methods of expressing the concentration of solutions or solventswhich are not
commonly used. Some of them are tabulated here in Table 5.1.

Table 5.1 summary of Concentration Expression

Unit Symbol Definition Relationship

Molarity M Number of moles of
solute per litre of M= ( )
solution
Molality M Number of moles of m=
solute per kilogram of
solution
Mole Fraction X Ratio of the moles of X=
solute to the total

57
 moles of solute plus
solvent
Normality N Number of equivalent N=
of solute per litre of
solution
Percent by weight Wt % Parts by weight of Wt %=
solute per 100 parts
by weight of solution.
Percent by Volume Vol% Parts by weight of Vol%=
solute per 100 parts
by volume of solution

PRACTICE QUESTIONS
1. What volume will the following gases occupy at STP
i) 42g of N2
ii) 16g of O2
iii) 0.2mol of CO2
iv) 3.02 x 1023 molecules of CO
v) 1.20 x 1023 molecules of CH4

2. (a) How many moles are present in 1g of sodium hydroxide?

(b) What is the mass of 1.0mol of oxygen atoms?
3. Using 12g of copper, what mass of Copper (ii) trioxonitrate (v) will be formed in the
reaction
3Cu + 8HNO3 3Cu(NO3)2 + 2NO + 4H2O
Cu = 63.5, O = 16, N = 14, H= 1)
4. How many moles are contained in 47g of magnesium trioxonitrate (v) Mg(N0 3)2
(a) How many molecules of Mg(NO3)2 are in the sample
(b) How many moles are there in:
(i) 6g of magnesium
(ii) 6g of oxygen gas

58
 CHAPTER 6
STATE OF MATTER AND THE GAS LAWS

Matter is defined as anything that has mass and occupies space. Matter is everything on earth
including the universe itself. They include.
1. Things too small to be seen with our naked eyes e.g. atoms, protons, electrons, ions,
amoeba, etc
2. Things we cannot even see at all but can be detected by other means e.g. rays, gas, air, etc.

Experimental results have proved that matter contains positive and negative charges. Since matter
appear to be uncharged, it then means that matter contain equal numbers of positive and negative
charges.

6.1 STATE OF MATTER

The three physical states of matter are
1. SolidState: Here the particles are held in position by strong inter-particular (cohesion) force.
Hence solid state matter
i. Have a fixed position
ii, Have a definite volume and shape
iii. Have only enough kinetic energy to vibrate
v. Not compressible.
vi.
2. LiquidState: Here the particles inter-particular (cohesion) forces are not as strong as in the
solid state. Hence the liquid state matter
i. does not have a fixed position
ii. Have a definite volume but not a definite shape.
iii. Have enough kinetic energy to vibrate and translate.
iv. Not compressible.

3. Gaseous State: Here the particles are far apart and the forces of attraction between them are
very weak. Therefore, the gaseous state matter:

I. Does not have a fixed position

II. Does not have a definite volume nor shape
III. Have enough kinetic energy to vibrate and translate
IV. Compressible.

It should be noted that when the heat content in matter is altered, matter changes from one state
to another. Also, some matters changes from solid to gaseous state directly and vice versa
without passing through the liquid state. Such matters are said to sublime.

6.2 THE GAS LAWS

The Gas Laws provides the description of the ideal gas behaviour based on experimental works
by notable scientists like Boyle, Charles, Dalton and Graham.

59
6.2.1 THE KINETIC THEORY OF GASES
The Kinetic theory of gases states that:

i. Gaseous particles are very tiny.

ii. Gases have negligible force of attractions because their molecules are far apart.

iii. Gases also have negligible volume because their molecules arc so tiny, far apart, and with
empty spaces between them, making their actual volume very little compared to their
containing vessels.

iv. The gas molecules are always in a state of random motion hence the total kinetic energy
of the entire gas molecule in a container at constant temperature and pressure is constant.

v. The pressure exerted by a gas depends on the contact collision of the gas molecules with
themselves and with the walls of the containing vessels.

6.2.2 BOYLE'S LAW

Boyle's law was put forward by an Irish scientist Robert Boyle in the 1600s. It states that the
volume of a given mass of gas is inversely proportional to its pressure provided temperature
remains the same (constant). That is, as volume is increasing, the pressure will be decreasing at
the rate in which the volume is increasing and vice versa. This means if the volume is doubled,
the pressure will be halved. And the product of the two variables (i.e. volume and pressure) will
always remain the same (i.e. constant).

The law can be expressed mathematically as V

-V =
K = VP

Where
V = Volume of the gas sample
P = Pressure exerted by tile gas sample.
K = Constant

This law can be shown to be true by confining a known volume of air in cylinder with a movable
piston.As the volume of the gas is varied, the resultant change in pressure is read and recorded.

From the results, it will be observed that as volume is halved, pressure is doubled and vice versa.
And the product of pressure and volume is always the same.

V1 P1 = V2 P2 = V3 P3

60
Table 6.1: Experimental Data Illustrating Boyle’s Law

e Volume Pressure Volume x Pressure

1 100.0cm3 10.0 atm 1000 atm cm-3
2 500.0cm3 2.00 atm 1000 atm cm-3
3 250.0cm3 4.00 atm 1000 atm cm-3
4 125.0cm3 8.00 atm 1000 atm cm-3
5 62.5cm3 16.00 atm 1000 atm cm-3

Figure 6.1: Graph illustrating Boyle’s law (Gas pressure – Volume relationship). A plot of
Volume versus Pressure

Figure 6.2: Boyle‟s law experiment (a) The volume at 1 atm pressure is 1.0L (1000cm3) (b)
When pressure is doubled to 2 atm, the volume will be halved (0.5L or 500cm 3). Tripling the
pressure will reduce the volume to one-third of the original volume

61
6.2.3 CHARLES LAW

The relationship between gas volumes and temperature at constant pressure was put forward by a
French scientist Jacques Charles in the l700s. The law states that: The volume of a given mass of
gas is directly proportional to its absolute (Kelvin) temperature if the pressure remains the same
(constant). That is as the volume is increasing, the temperature will equally increase and vice
versa. And in every case, the value obtained by dividing the volume by the Kelvin temperature is
always the same.

The law can be expressed mathematically as V T

V = KT

Rearranging, we get
= K (At a constant pressure)

Where
V = Volume of the gas sample
T = Kelvin temperature of the gas sample
K = the constant

Charle‟s law
0 Kelvin (absolute
zero)

The relationship between the gas volumes and temperature can be demonstrated by confining a
gas in a cylinder with a weighted piston. Here, the pressure exerted by the gas is equal to the
pressure exerted on the gas by the weighted piston which is not moving.

As the temperature is increased by heating, the gas will expand, forcing the weighted piston
upward so as to give the gas an increased volume. Also, when the temperature of the cylinder is
reduced by cooling, the gas will contract, forcing the weighted piston downward to assume a
reduced gas volume

Figure 6.3

62
Charles experiment: At constant pressure, if temperature is doubled, the volume will be
increased to two times the original volume.

From the results of the experiment, it is observed that at every change in temperature, the volume
changed, in the same direction. That is, increased temperature gave increased volume and vice
versa. And for every trial, the value obtained by dividing volume by Kelvin temperature was
always, the same:
i.e. = =

6.2.4 GENERAL GAS EQUATION

This is a mathematical statement, which combines Boyle's law and Charles law. This equation is
used by chemist to investigate what the volume of gases will be when both their temperature and
pressure are changed. It is used to solve problems in which all the three variables volume,
pressure and temperature change.

From Boyle‟s law:

V

Combining both laws we get:

V
-V = K re-arranging we get:

=K

= =

63
6.2.5 STANDARD TEMPERATURE AND PRESSURE (STP)
As the volume of a sample of gas depends on the temperature and pressure, therefore for
comparing volumes of gases, a standard temperature and pressure are used. The standard
temperature is 0°C (273K) while the standard pressure is 760 mmHg (101.3 x 103pa). The
standard temperature and pressure can also be called STP

Example 6.1
A certain mass of gas occupies 100cm3 at 255mmHg. What will be its volume at 390mmHg,
assuming no change in temperature.

Solution
The question involves only the gas volume and pressure. Therefore, Boyle‟s law mathematical
expression will be used in solving the problem.

V1P1 = V2P2
Initial gas volume V1 = 100cm3
Initial gas pressure P2 = 255mmHg
Final gas volume V2 = unknown
Final gas pressure P2 = 390mmHg

Make the unknown value subject of the formula

=

V2 =

V2 = = 130.77cm3

6.2.7 DALTON'S LAW OF PARTIAL PRESSURES

Dalton's law of partial pressures states that the total pressure of a mixture(non-reacting gases) of
ideal gases is the sum of all the individual pressures of the gases only when they occupy the
same volume:

P = PA + PB + PC

Note that a mixture of gases contains two or more gases which do not: react chemically together.
Also, the partial pressure is the pressure exerted by each of the gases in the mixture.

That is, the total pressure of a mixture of 1dm3 of oxygen at 100mmHg and 1dm3 of nitrogen at
200mmHg will be 300mmHg.

64
6.2.8 GRAHAM'S LAW OF DIFFUSION
Graham's law of diffusion state that at constant temperature and pressure, the rate of diffusion of
a gas is inversely proportional to the square root of its density. Molecular masses can also be
used in terms of the density. Graham's law mathematical expression is:

R1 =
√

=√ OR =√

R1 and R2: Initial and final rate of diffusion

d1 and d2: Initial and final densities of gases
m1 and m2: Initial and final molecular mass of gases

Example 6.2
What is the total pressure exerted by the mixture of l dm3 of oxygen at 320mmHg. 1dm3 of
nitrogen gas at 230mmHg

Solution
According to Dalton„s law of partial pressure, the total pressure will be the sum of all the
individual partial pressures since they occupy the same volume.
P = Poxygen + Pnitrogen
P = (320 + 230) mmHg = 530mmHg

Example 6.3
A volume of 3dm3 of nitrogen is mixed with a volume of 2dm3 of oxygen, with both at the same
pressure of l01.3mmHg. What is the partial pressure of each gas in the mixture?

Solution
Gas A (nitrogen)
V1 = 3dm3 P1 = 101.3
V2 = 5dm3 P2 = x

P2 =

P2 = = 60.78mmHg

Gas A (Oxygem)
V1 = 2dm3 P1 = 101.3

65
V2 = 5dm3 P2 = x

P2 =

P2 = = 41.32mmHg

Example 6.4
A volume of nitrogen gas at 300 mmHg is 450cm3. The gas is connected to oxygen at
400mmHgwith a volume of 550cm3. What is the pressure of the mixture, assuming temperature
is constant?

Gas A (nitrogen)

V1 = 450cm3 P1 = 300mmHg
V2 = 1000cm3 P2 = x

P2 =

P2 =

Gas A (Oxygen)
V1 = 550cm3 P1 = 400mmHg
V2 = 1000cm3 P2 = x

P2 =

P2 =

PT = PN2 PO2
PT = 135mmHg 220mmHg
= 355mmHg

Examples 6.5
Calculate the rate of diffusion of methane (CH4) and sulphur dioxide (SO2).

Solution
The gases densities is not reflected in the question and in solving this problem the expression of
Graham law that contains molecules masses showed be used because molecular‟ masses are
easily determined from atomic masses.

66
 =√

R1 = Rate of diffusion of CH4

R2 = Rate of diffusion of SO2
M1 = Molecular mass of CH4 = 16
M2 = Molecular mass of SO2 = 64

=√

=√

From the results, it shows that the rate of diffusion of methane CH4 is twice that of sulphur
dioxide.

PRACTICE QUESTIONS
1. What conditions are called the standard temperature and pressure (s.t.p) for
measuring gases? (b) What is the molar volume of gases at s.t.p.?

2. The volume of a given mass of gas is 804cm3 at temperature of 127°C. Calculate the
temperature of the gas when its volume is reduced to 603cm3 while the pressure
remains constant.

3. A gas sample has a volume of 210dm3 at 37°C and 106.6mmHg. What would its
final temperature be if the volume is reduced to 170dm 3 and at a pressure of
76.4mmHg ;

4. A gas has a volume of 120dm3 at a pressure of 73.6mmHg and a temperature of

30°C. At what: pressure will the gas be when its volume is halved and at a constant
temperature.

5. The maximum capacity of a container is 200cm3. If the container has a volume of 145cm3
at 20oC, will an increase of temperature to 45°C increase the volume of the container to
its maximum capacity assuming the pressure of the container is constant.

6. 600cm3 of nitrogen gas at 300mmHg is mixed with 400cm3 of oxygen at 500mmHg. Find
the partial pressures of each gas and total pressure of the mixture when the temperature is
kept constant·

7. (a) What gas law combines Boyle's Law and Charles Law?
(b) Show its mathematical derivation.

67
 CHAPTER 7
CHEMISTRY OF THE GROUP 1, 2 AND 3 ELEMENTS

S – BLOCK ELEMENTS

The alkali and alkaline earth metals are the s-block elements because their outermost electrons
are found in the s-subshells. The alkali metals are in the group one and they have one electron in
their outermost s-subshell while the alkaline earth metal have two electrons and are in group two.

7.1 GENERAL OBSERVATIONS ABOUT THE MAIN – GROUP ELEMENTS

In studying the chemistry of the main group elements, there are some general trends observed.
These periodic trends are discussed below:
Elements of the left side of the periodic table are mainly metals, while those on the right side of
the periodic table are non-metals. Ionization energies and electronegativities are low for metal as
compared to nonmetals. So the metal tend to lose their valence electrons to form cations (e.g.
Na+, Ca2+, Al3+) in compounds or in aqueous solution. On the other hand, nonmetals react by
gain of electrons to form monoatomic anions (O2-, Cl-) and Oxoanions (NO3-,SO42-).

Also, oxides of metals are basic; they dissolve in water to give basic solution.

Na2O(s)+ H2O (i) → 2NaOH(aq)

It should be noted however that oxides of metal in high oxidation states e.g. in some transition
metals, can be acidic; chromium (IV) oxide, CrO3 is an acidic oxide. Oxides of nonmetals are
acidic they dissolve in water to give an acidic solution

SO3(g) + H2O(i) → H2SO4(aq)

Generally, metals have oxidations states equal to the group number, which corresponds to a loss
of the valence electrons in forming compounds. Some metallic elements in the fifth and sixth
periods also have oxidation states equal to the group number minus two (e.g. Pb2+). On the other
hand, non-metals (apart from fluorine and oxygen which are highly electronegative) have
variable oxidation states, stretching from the group number (the most positive value) to the group
number minus eight (the most negative value). As an illustration, Chlorine (a Group VII element)
has the following oxidations states in compounds; +7, +5, +3, +1, and -1.

The metallic and nonmetallic character of elements changes gradually, in definite ways from left
to right across the period and down the group. Generally, metallic character decreases from left
to right across the period. While the metallic character increases down the group. This trend is

68
more obvious with the Group III A – VA elements. For examples, in group VA, Carbon is a
nonmetal, silicon and Gallium are metalloids, while tin and lead are metals. Reactivity increases
down the metallic group. For example, in the Group IA elements; lithium is much less reactive
than sodium and potassium. For nonmetals, reactivity decreases down the nonmetallic group, for
example fluorine is far more reactive than bromine and iodine.

A second-period element is often rather different from the other elements in its group. The
reason for this is that the second period elements generally have small atoms that tend to hold
electrons strongly, resulting to high electronegativity. For example while the electronegativity of
nitrogen is 3.1, the other member of the group VA have electronegativities values within 1.9 –
2.1.

Another reason why the second – period elements behave differently from the remaining
members of their group is that the second period elements involves only the s-and p orbital‟s in
bond formation, which places a limit on the types of compounds they form. The remaining
elements in the group involve the use of the s, p and d-orbital indicating that more types of
compounds can be formed by these elements. For example, Nitrogen as a second-period element
forms only the trihalides (e.g. NCl3) while phosphorus has both the trihalides (PCl3) and
pentahalides (PCl5) which it forms using the 3d orbital.

7.2 GROUP 1 – THE ALKALI METALS

The alkali metals are member of the group 1 elements. They have valence shell electronic
configuration as ns1

The alkali metals are chemically the most reactive metal and their reactivity increases as the
group decend. This is because the single outer electron is increasingly screened from the positive
charge of the nucleus by successive electron shells and so is lost more and more readily. Because
the metal is very reactive, it occurs in nature combined with other elements.

The alkali metals are soft and white with a characteristic luster or sheen when freshly cut, this
surface tarnishes very rapidly with the formation of a thin layer of the oxide. Table 7.1 shows
members of the alkali metals and their electronic configuration.

Table 7.1Group 1 elements and their electronic configuration

ELEMENTS ELECTRONIC CONFIGURATION

Lithium Li 3 - 1S2 2S1
Sodium Na 11 – 1S2 2S2 2P6 3S1
Potassium K 19 - 1S2 2S2 2P6 3S23p64s1
Rubidium Rb 37 - (Kr) 5s1
Caesium Cs 55 - (Xe) 6s1
Francium 87 - (Rn) 7s1

69
The atoms of the elements get larger down the group as more shells of electrons are added,
screening the outer electrons from the increasing nuclear charge. Atoms of elements down the
group are more likely to have electrons densities transferred away from them in a chemical
reaction than atoms of element up the group. This is reflected in the decreasing
electrongegativity of the elements down the group.
Atoms of the elements down the group are held together less strongly than those higher up,
leading to lower melting points and alsoreducing the strength of the metallic bond. Table 7.2
shows the physical properties of the group 1 elements.

Table 7.2The physical properties of the group 1 elements

Element Li Na K Rb Cs
Metallic radius/nm 0.16 0.19 0.24 0.25 0.27

Ionic radius/nm 0.074 0.102 0.138 0.149 0.170

Electrongativity 1.0 0.9 0.8 0.8 0.7

1st Ionization energy/kj 520 496 419 403 376

mol
7298 4563 3051 2632 2420
nd
2 Ionization energy
181 98 63 39 29
0
Melling points/ c
1342 883 760 686 669
0
Boling points/ c
0.53 0.97 0.86 1.53 1.88
-3
Density/gcm

The group 1 elements have similar electronic configuration in which each has a single electron
outside a full shell of inner electrons. This similarity in their electronic configuration directly
influences their chemical properties since it determines the way in which they form chemical
bond. The similarities in chemical behaviour on them includes

(a) Reactivity: - They are chemically the most reactive metals. They are so reactive that they
are generally found in nature combined with other elements and the pure metals are
usually stored in an inert liquid out of contact with air or water.

The alkali metals react with cold water, displacing hydrogen and forming an alkaline
hydroxide solution

2M(s) + 2H2O(l) H2(g) + 2MOH(aq)

70
 2Na(s) + 2H2O(l) H2 + NaOH(aq)

(b) Univalence:- They all have a single electron in their outer s-subshell which is readily
lost to form ions with a noble gas configuration and a single positive charge e.g. Na+, Li+
etc. The alkali metals thus have only one oxidation state, +1

(c) Formation of ionic Compound: - Evidence from the ionization energies of elements
suggests that there is a particular stability associated with the electronic configuration of
the noble gases. In order for the group 1 elements to achieve this full shell configuration,
they give away the single electron in their sub-shell to become M+ ion. This involves the
complete transfer of electron from the atom of the group one element to another atom of
another group of element. This relationship is called ionic or electrovalent bond and the
compound formed is called ionic compound.

(d) Strong Reducing Agent: - As a reducing agent, they are oxidize in the cause of a
chemical reaction by

(i) Loss of electron

(ii) Increase in oxidation number

(iii) Addition of oxygen

4Na(s) + O2(g) 2Na2O(s)

From the equation, electrons are removed from sodium and transferred to oxygen. Also oxygen
is added to sodium. Therefore we say that sodium is oxidized while oxygen is reduced.

(d) Low Ionization Energy: - Ionization energy is the energy needed to remove one mole of
electron from one mole of a gaseous atom or gaseous cation. Ionization energy increases
across the period, as it becomes harder to remove an electron due to the increasing
positive charge across the period without the additional electron shells to screen the outer
electrons. The atomic radius gets smaller and electrons are held more firmly.

(e) They all burn in air in strongly exothermic reaction producing typical flame colours.

7.3 CHEMICAL PROPERTIES OF THE ALKALI METALS

1. They tarnish in damp air to form their oxides when these oxides react with water; it forms
the corresponding hydroxides, which slowly absorb atmospheric carbondioxide to form
crystals of hydrated trioxocarbonate(iv) salt of the corresponding metal.

4M + O2 2M2O

M2O + H2O 2MOH

71
 2MOH + CO2 M2CO3 + H2

(M = alkali metal)

2. They react with water, liberating hydrogen and forming the corresponding hydroxide
solutions which are very basic.

2M + 2 H2O H2 + 2 MOH

The vigour of this reaction increases down the group. While lithium reacts slowly with water,
sodium react vigorously, potassium reacts violently with water that the hydrogen formed catches
fire. Rubidium and caesuim reacts explosively.

3. They react with dilute acids vigorously liberating hydrogen gas and forming the
corresponding salt.

2M + 2HCl H2 + 2MCl

4. When heated, they react with hydrogen to form the corresponding, hydrides.

2M + H2 2M+H.

5. They react violently with halogens forming the corresponding halides

2M + Cl2 2MCI

6. They dissolve in mercury forming the corresponding amalgams which are used as
reducing agent
M + Hg M/Hg

7. They dissolve in liquid ammonia and some amines to form a blue solution. At higher
concentration, the solutions are copper, coloured
M + NH3 M+NH2- + ½ H2

7.4 THE GROUP II ELEMENTS: – THE ALKALINE EARTH METALS

The group II elements are also very reactive metals in which the electropositive character
increases down the metallic group. The element in this group has two electrons in their outer
shell hence less reactive and harder than the group I elements, as they need more energy to lose
the outer two electrons to achieve a noble gas configuration. They all burn in air in strongly
exothermic reaction. Some of them produce typical flame colours. Apart from beryllium, which
differs from the other alkaline earth metals in its lack of reactivity, alkaline earth metals react
with cold water, displacing hydrogen and forming an alkaline hydroxide. Also, apart from
beryllium, the alkaline earth metals are white, relatively soft metals, which are good conductors
of heat and electricity. Table 7.3 shows the members of the group and their electronic
configuration.

72
Table 7.3 The group II element and their electronic configuration.
ELEMENT ELECTRONIC CONFIGURATION
Beryllium Be 4 – 1s2 2s2
Magnesium Mg 12 – 1s2 2s2 2p63s2
Calcium Ca 20 – 1s2 2s2 2p2 3s2 3p2 4s2
Strontium Sr 38 –(Kr) 5s2
Barium Ba 56 – (Xe)6s2
Radium Ra 88 – (Rn) 7s2

They form basic oxides and hydroxides with general formula MO and M(OH)2. Their oxides and
hydroxides are either sparingly soluble or insoluble.

The freshly cut surfaces are shiny, but they quickly oxidize and the oxide film protects the metal
from further reaction.

The group II element ionizes with the loss of two electrons to form ions with oxidation number
of +2 e.g. Ca2+, Mg2+ etc.

Like the alkali metal, the ionization energy and the electronegativity of the alkaline earth metals
decrease down the group-as the number of shell increases, the attractive pull of the nucleus to the
outer electrons decreases, as the electron are screened more effectively from the positive charge
of the nucleus.

Like he alkali metals, metals down the group are held together less strongly than those higher up,
leading to lower melting point. The strength of the metallic bond also decreases down the group
as the density of the positive ions in the metal lattice decreases as the ion get larger. Also
reactivity increase down the group as the element at the bottom of the group are more reactive
and softer than those on top.. For example, Barium in the six period react with water much like
the alkali metals. It is also a soft metal much like the alkali metals. Magnesium in the third
period is a less reactive and harder metal.

7.5 SIMILARITIES BETWEEN ALKALI AND ALKALINE EARTH METALS.

1. They are both high up in the electrochemical series hence good reducing agent.

2. They both react with water, reducing it to hydrogen and the metal hydroxide.

Group (1) 2M + 2H2O 2MOH + H2

Group (2) M +2H2 O M(OH)2 + H2

3. They both have their valence shell electrons in the s-subshell.

73
4. They both show one oxidation state.

5. The nitrates of all the s-book elements decompose on heating with a bunsen flame.

6. The s-block elements are so reactive that they are not found free in nature. And they are
extracted from there ore by electrolysis.

7. Their hydroxides decompose to form the corresponding oxide and water.

Group (1) 2MOH M2O + H2O

Group (2) M (OH)2 MO + H2O

8. They are soft and easily cut with a knife

9. They both have low melting and boiling points

10. They have low densities (Li, Na, K,) are less dense than water
11. They have low standard enthalpies (heats) of melting and varpourisation
12. They show typical flame colours; Li – red, Na – yellow, K, - lilac, Rb – , Cs, - blue, Be –
colourless, Mg, - Brilliant white, Ca – Brick red, Sr – crimson

7.6 DIFFERENCE BETWEEN ALKALI AND ALKALINE EARTH METALS.

1. The alkali metals are more electropositive than the alkaline earth metals.
2. The alkali metals have one electron in their outer shell while the alkaline earth metals
have two.
3. The group II elements show stronger metallic bonding than the group I. This is reflected
in their properties
4. All common group I metal salts are soluble in water. All group II salts where the anions
have a charge of – 1 are soluble, with the exception of hydroxides. All group II salts
where the anion has a charge of – 2 are insoluble with the exception of a few magnesium
and calcium salts.
5. Group I nitrates except Lithium decompose on heating to give stable nitrite while group
II nitrates give oxide

Group (I) 2NaNO3(s) 2Na NO2(s) + O2(g)

Group (II) and Lithium

4 Li NO3(s) 2 Li2O(s) + 4NO2(g) + O2(g)

Mg (NO3)2(s) 2 MgO(s)+ 4NO2(g) + O2(g)

6. The compounds of Group I metals are thermally more stable than those of group II
metals. The carbonates and hydroxides of Group 1 metals (except Li2CO3 and LiOH) do

74
 not decompose at 1000oC, but those of group II metals decompose to their oxides on
heating.

Li2CO3 Li2O + CO2

CaCO3 CaO + CO2

2LiOH Li2O + H2 O
Ca(OH)2 CaO + H2 O

As stated earlier (section7.1),a second period element show properties that aredifferent from its
group. These differences are more obvious in the right side of the periodic table. For example:

Lithium though in group I resembles group II because it shows similar properties with the group
II elements.

1. When heated in an ordinary Bunsen flame the group I carbonates are stable with the
exception of lithium carbonate, Li2CO3. The group II carbonates together with lithium
carbonate decomposes to form stable oxides, with the liberation of carbon dioxide gas

Ca CO3(s) CaO(s) + CO2(g)

Li2 CO3(s) Li2O(s) + CO2(g)

2. Group I nitrates, with the exception of lithium nitrate LiNO3 decompose on heating on a
Bunsen flame to give their corresponding nitrite and these(NaNO2) are stable to heat.

2Na NO3(s) 2 NaNO2(s) + O2(g)

In contrast, lithium nitrate and all the group II nitrates decompose on heating to form the
corresponding oxide.

4 LiNO3(s) 2Li2O(s) + 4NO2 + O2(g)

2Mg (NO3)2(s) 2MgO + 4NO2 + O2(g)

3. Li2CO3 is only slightly soluble in water at room temperature, whereas sodium carbonate
and other group I elements carbonate are soluble

Also, beryllium differs from the other members of its group by its lack of reactivity. Further-
more, while the hydroxides of magnesium and barium are basic, beryllium hydroxide is
amphoteric, reacting with both acids and bases.

7.7 THE GROUP III ELEMENTS

The group III elements mark the beginning of the p-block elements. These elements have three
electrons in their outer shell, two in the s-subshell and one p-subshell. Their valence shell

75
electronic configuration is represented as ns2 np1. The principal oxidation state of the Group III
elements is +3. Table 7.4 below shows the members of the group and their electronic
configuration.

Table 7.4 The Group III elements and their electronic configurations.
Elements Symbol Electronic Configuration
Boron B 5 – 1s22s22p1
Aluminium Al 13 – 1s2 2p6 3s23p1
Gallium Ga 31 – (Ar) 3d10 4s2 4p1
Indium In 49 - (Kr) 4d10 5s2 5p1
Thalium Ti 81 – (Xe) 5d10 6s2 6p1

There is a gradation in the properties of these elements as we go down the group. This gradation
of properties can be explained in terms of:

7.7.1. METALLIC CHARACTERISTICS: - Metallic character increases down the group,

from Boron which shows clearly non-metallic properties, through aluminium which shows
amphoteric properties to the rest of the elements (gallium, indium and thallium) which are metals
and also show metallic character.

In common with other reactive metals, aluminium will give off hydrogen gas with hydrochloric
or sulphuric acids. But it does not react with nitric acid because the acid render‟s the aluminum
surface passive. Boron does not give of hydrogen with sulphuric and nitric acid instead the
boron reduces the acid

2B + HNO3 2H3BO2(aq)+ 6NO2(g)

Boron, aluminium and gallium all show an oxidation state of +3 in their compounds whileindium
and especially thalium prefers an oxidation number of +1. These properties of the group shows
clearly that metallic property of the elements increases as one go down the group.

7.7.2 NATURE OF THEIR BOND

Bonding in boron is covalent. The atom shares its 2s2 2p1 valence electrons to attain a full
valence shell configuration, with oxidation state of +3. Aluminium also form many covalent
compounds (e.g. AlCl3) as well as ionic ones e.g. AlF3 with +3 oxidation state. But gallium,
indium and thallium form predominantly ionic compounds with oxidation states of +1.
The elements in this group all form halides with the general formular MX3 e.g. BCl3,
AlCl3, GaCl3. Some of these chlorides dimerise e.g. aluminium trichloride gives Al2Cl6 with a
mixture of both covalent and coordinate bonding. Boron chloride (BCl3) and aluminium
chloride (AlCl3) are covalent, hence they show nonmetallic character. Indium and especially
thallium which prefer an oxidation state of +1 will prefer an ionic bond.

7.7.3. RELATIVE STABILITY OF THEIR OXIDATION STATES:-

The metallic behavior of an element deceases as the positive oxidation number of its elements in
compound increases. Thus as the +1 oxidation state becomes more stable down the group so is

76
the increase in their metallic properties.
The +1 oxidation state increases down the group because increase in electronic shell screens
the valence shell electrons from the attractive nuclear pull. Therefore, covalent bonding does not
form between large atoms. Here, the s-electrons remain inert and do not take part in bonding,
while the p-electron becomes easily lost to form ionic bond. So the +1 oxidation state becomes
more stable than the +3 oxidation state down the group.

7.7.4 ACIDIC / BASIC NATURE OF THEIR OXIDES: - All the elements give oxides
with general formula E2O3

Boron burns in oxygen at 700oC to form boric oxide B2O3 which dissolves in hot water to form
boric acid. B2O3 + 3H2O 2H2BO3

Boric acid and boric oxide reacts with metal oxide or hydroxide to form borates (borates are salts
of oxyacide of boron). This clearly shows that boron exhibits nonmetallic properties

Aluminum reacts with oxygen to form aluminium oxide (alumina)

4Al +3O2 2Al2O3

Aluminum oxide shows amphoteric properties as it reacts with both acids and bases. It forms
simple aluminuim salts with acids.
Al2O3 + 6HCl 2AlCl3 + 3H2O

While it reacts with bases to form the corresponding metal aluminates.

Al2O3 + 2NaoH + H2O 2NaAl(OH)4

77
PRACTICE QUESTIONS

1. (a) Give an account of how lithium, though in Group 1 behave like the Group
II elements.
2. (a) Write balanced chemical equation for the following reactions:

(i) K + H2O
(ii) Mg(NO3)2(s) heat
(iii) Mg +Cl2
(iv) LiNO3(s) heat
(v) CaCO3(s) heat
(vi) LiCO3(s) heat

3. Explain why and how beryllium though a group II element does not behave like the other
members of its group

Explain why the ionization M+ + e- takes place more readily as you pass down the group I
elements.

78
 CHAPTER 8
ELECTROCHEMISTRY
Electrochemistry

Electrochemistry is best defined as the study of the interchange of chemical and electrical
energy. It is primarily concerned with two processes that involve oxidation–reduction reactions:
the generation of an electric current from a spontaneous chemical reaction and the opposite
process, the use of a current to produce chemical change.

Terms Associated with Electrochemistry

Cell Notation

An electrochemical cell consists of two half-cells, which can be represented by cell notation. An
example of electrochemical cell is the Daniel Cell. The Daniel cell is composed of two half
cells. It is represented by the cell notation:

Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)

The anodic half is written first on the left hand side.

The single line denotes the boundary between a metal and its ions in solution.
The double line represents the porous partition or salt bridge.

Standard Electrode Potentials (Reduction Potentials)

The standard electrode potential of a cell is the potential difference or voltage of the cell at
equilibrium under standard conditions. Under such standard condition, the anode is a standard
hydrogen electrode, where hydrogen is oxidized:

½ H2(g) → H+(aq) + e−

The cathode reaction is the half reaction that is been considered.

79
The electrode potential is also known as the reduction potential E0red. The reduction potential
expresses the tendency of the oxidizing agent to be reduced (i.e the ease with which an oxidizing
agent gains electron and become reduced).

Hydrogen is assigned a value of zero. Oxidizing agents stronger than H+ (i.e lower than
hydrogen in the electrochemical series) have positive values e.g (F2 = +2.866 V) and negative for
oxidizing agents that are weaker than H+ (e.g., −0.763 V for Zn2+).

Mathematically, the potential difference of a cell in a redox reaction is given as

E0cell = E0cathode – E0anode

E˚ cell = E ˚ reduced - E ˚ oxidised

= E ˚ right - E ˚ left

Question 1

What is the EMF of the Daniel Cell represented by the notation:

Zn(s)/ Zn2+(aq)// Cu2+(aq)/Cu(s)

Given that:

Zn2+ + 2e- → Zn(s); E ˚= -0.76V

Cu2+ + 2e- →Cu(s); E ˚= +0.34V

Solution: E˚= E˚ cathode – E˚ anode

= 0.34 – (-0.76)

= 0.34 + 0.76 = 1.10V

Electrochemical Cells

80
A device for producing an electrical current from a chemical reaction (redox reaction) is called
an electrochemical cell.

Voltaic Cells

A Voltaic cell, also known as a galvanic cell is one in which electrical current is generated by a
spontaneous redox reaction. A simple voltaic cell is shown below. Here the spontaneous reaction
of zinc metal with an aqueous solution of copper sulphate is used.

Zn + Cu2+⎯⎯→ Zn2+ + Cu

A bar of zinc metal (anode) is placed in zinc sulphate solution in the left container. A bar of
copper (cathode) is immersed in copper sulphate solution in the right container. The zinc and
copper electrodes are joined by a copper wire. A salt bridge containing potassium sulphate
solution interconnects the solutions in the anode compartment and the cathode compartment.

The oxidation half-reaction occurs in the anode compartment.

Zn ⎯⎯→ Zn2+ + 2e–

The reduction half-reaction takes place in the cathode compartment.

Cu2+ + 2e– ⎯⎯→ Cu

Anode

81
When the cell is set up, electrons flow from zinc electrode through the wire to the copper
cathode. As a result, zinc dissolves in the anode solution to form Zn2+ ions. The Cu2+ ions in the
cathode half-cell pick up electrons and are converted to Cu atoms on the cathode. At the same
time,

SO42- ions from the cathode half-cell migrate to the anode half-cell through the salt bridge.
Likewise, Zn2+ ions from the anode half-cell move into the cathode half-cell. This flow of ions
from one half-cell to the other completes the electrical circuit which ensures continuous supply
of current. The cell will operate till either the zinc metal or copper ion is completely used up.

Daniel Cell

It is a typical voltaic cell. It was named after the British chemist John Daniel. It is a simple zinc
copper cell like the one described above.

82
In this cell the salt-bridge has been replaced by a porous pot. Daniel cell resembles the above
voltaic cell in all details except that Zn2+ ions and SO42- ions flow to the cathode and the anode
respectively through the porous pot instead of through the salt-bridge. Inspite of this difference,
the cell diagram remains the same.

Cell reaction

The flow of electrons from one electrode to the other in an electrochemical cell is caused by the
half-reactions taking place in the anode and cathode compartments. The net chemical change
obtained by adding the two half-reactions is called the cell reaction. Thus, for a simple voltaic
cell described above, we have

(a) Half-reactions:

Zn(s)⎯⎯→ Zn2+(aq) + 2e

Cu2+(aq) + 2e– ⎯⎯→ Cu(s)

(b) Cell reaction by adding up the half-reactions:

Zn(s) + Cu2+(aq)⎯⎯→ Zn2+(aq) + Cu(s)

Cell potential or EMF

The flow of current through the circuit is determined by the „push‟, of electrons at the anode and
„attraction‟ of electrons at the cathode. These two forces constitute the „driving force‟ or
„electrical pressure‟ that sends electrons through the circuit.

83
This driving force is called the electromotive force (abbreviated emf) or cell potential. The emf
of cell potential is measured in units of volts (V) and is also referred to as cell voltage.

Cell diagram or Representation of a Cell

A cell diagram is an abbreviated symbolic depiction of an electrochemical cell.

IUPAC Conventions. In 1953 IUPAC recommended the following conventions for writing cell
diagrams. We will illustrate these with reference to Zinc-Copper cell. It may be noted that the
metal electrode in anode half-cell is on the left, while in cathode half-cell

(1) a single vertical line (|) represents a phase boundary between metal electrode and ion
solution (electrolyte). It is on the right of the metal ion.

(2) A double vertical line (||) represents the salt bridge, porous partition or any other means of
permitting ion flow while preventing the electrolyte from mixing.

(3) Anode half-cell is written on the left and cathode half-cell on the right.

(4) In the complete cell diagram, the two half-cells are separated by a double vertical line
(salt bridge) in between. The zinc-copper cell can now be written as

(5) The symbol for an inert electrode, like the platinum electrode is often enclosed in a
bracket.

For example,

Mg /Mg2+/H+/H2 (Pt)

(6) The value of emf of a cell is written on the right of the cell diagram. Thus a zinc-copper
cell has emf 1.1V and is represented as

Zn /ZnSO4// CuSO4/ Cu E = + 1.1 V

84
 Convention regarding sign of emf value

Thus the emf of the cell is given the +ve sign. If the emf acts in the opposite direction
through the cell circuit, it is quoted as –ve value. For example, Daniel cell has an emf of
1.1V and the copper electrode is positive. This can be expressed in two ways :

The negative sign indicates that the cell is not feasible in the given direction. The reaction
will take place in the reverse direction.

Calculating the emf of a cell

The emf of a cell can be calculated from the half-cell potentials of the two cells (anode and
cathode) by using the following formula

Ecell = Ecathode – Eanode

= ER – EL

where ER and EL are the reduction potentials of the right-hand and left-hand electrodes
respectively.

It may be noted that absolute values of these reduction potentials cannot be determined. These
are found by connecting the half-cell with a standard hydrogen electrode whose reduction
potential has been arbitrarily fixed as zero.

Some important points concerning the Table of Standard Reduction Potentials

(1) The more positive the value of E°, the better the oxidising ability (the greater the tendency to
be reduced) of the ion or compound, on moving upward in the Table.

(2) The more negative the value of E° the better the reducing ability of the ions, elements or

compounds on moving downward in the Table.

85
 (2) Under standard conditions, any substance in this Table will spontaneously oxidise any
other substance lower than it in the Table.

USES OF ELECTRODE POTENTIAL

1. Predicting Feasibility of Reaction

The feasibility of a redox reaction can be predicted with the help of the electrochemical series.

The net emf of the reaction, Ecell, can be calculated from the expression

E°cell = E°cathode – E°anode

In general, if E°cell = + ve, the reaction is feasible
E°cell = – ve, the reaction is not feasible

Practice:

1. Predict whether the reaction

2 Ag(s) + Zn2+ (aq) ⎯⎯→ Ag+ (aq) + Zn(s)

is feasible or not. Consult the table for the E° values.

Given :

Ag/Ag+ Eo = 0.80V

Zn2+/Zn Eo = -0.763

solution

The cell half reactions are

Anode : 2Ag(s)⎯⎯→ 2Ag+(aq) + 2e– E° = 0.80 V

Cathode : Zn2+(aq) + 2e– ⎯⎯→ Zn(s) E° = – 0.763 V

E°cell = E°cathode – E°anode

E°cell = – 0.763 V – 0.80

86
= – 1.563

Since E°cell is negative, the given reaction is not feasible

2. Determine the feasibility of the reaction

2Al(s) + 2Sn4+(aq)⎯⎯→ 2Al3+ + 3Sn2+(aq)

Given

Al/Al3+ Eo = -1.66V

Sn4+/Sn2+ Eo= +0.15V

Solution

The given reaction consists of the following half reactions

Anode : 2Al(s) ⎯⎯→ 2Al3+ + 6e– E° = – 1.66 V

Cathode : 3Sn4+ + 6e– ⎯⎯→ 3Sn2+ E° = + 0.15

E°cell = 0.15 – (– 1.66)

= 1.81 V

Since E°cell is positive, the reaction is feasible.

2.Uses of electrode potential in predicting displacement reactions of aqueous salt

solutions

Metals near the bottom of the electrochemical series are strong reducing agents and are
themselves oxidised to metal ions. For example,

zinc lying down below the series is oxidised to Zn2+ ion, while copper which is higher up in the
series is produced by reduction of Cu2+ ion.

Zn ⎯⎯→ Zn2+ + 2e–

87
Cu2+ + 2e– ⎯⎯→ Cu↓

Thus when zinc is placed in CuSO4 solution, Cu metal gets precipitated. In general we can say
that a metal lower down the electrochemical series can precipitate the one higher up in the series.

3. Use of EP in predicting whether a metal will displace hydrogen from a dilute acid
solution

Any metal above hydrogen in the electrochemical series is a weaker reducing agent than
hydrogen itself and cannot reduce H+ to H2. Any metal lying below hydrogen is a stronger
reducing agent than hydrogen and will convert H+ to H2. This explains why Zn lying below
hydrogen reacts with dil H2SO4 to liberate H2, while Cu lying above hydrogen does not react.

Zn + H+ (dil H2SO4) ⎯⎯→ Zn2+ + H2 ↑

Cu + H+ (dil H2SO4) ⎯⎯→ Cu2+ + H2

CONCEPT OF ELECTROLYSIS

Electrolysis is the passage of a current (direct current) through an ionic substance that is either
molten or dissolved in a suitable solvent, producing chemical reactions at the electrodes and
decomposition of the substance.

Terms associated with electrolysis

Electrolyte: this is a substance that contains free ions, which carry electric current in the
electrolyte. The ions in a substance must be in a mobile state for electrolysis to occur.

Direct current (DC): this provides the energy necessary to create or discharge the ions in the
electrolyte. Electric current is carried by electrons in the external circuit.

Electrodes: they are electrical conductors (e.g metals, graphite) that provide the physical
interface between the electrolyte and the electrical circuit that provides the energy.

88
Faraday’s First Law of Electrolysis

The mass of a substance formed at an electrode during electrolysis is directly proportional to the
quantity of electricity that passes through the electrolyte.

Mathematically:

mαQ

where Q is quantity of electricity in coulomb

since Q = It

then m α It

m= EIt

E is a constant known as the electrochemical equivalent of the substance.

Faraday’s Second Law

Faraday‟s second law states that when the same amount of current is passed through different
electrolytes/elements connected in series, the mass of substance deposited at the electrodes is
directly proportional to their equivalent weight.
Differences Electrolytic cell Electrochemical cell
i. Electrical Structure There is supply of electricity No electrical supply.
(direct current).
i. Electrodes Metals can be the same or Both metals must be different
different
iii.Direction of electron flow From anode to cathode From the more
through external circuit electropositive metal to the

89
 less electropositive metal
iv.Energy transformation Electrical energy to chemical Chemical energy to electrical
energy
v.Reactions at the terminals Oxidation occurs at the Reduction occurs at the
positive terminal while positive terminal while
reduction occurs at the oxidation occurs at the
negative terminal negative terminal

90
 CHAPTER 9
9.0 REDUCTION OXIDATION REACTION

9.1 FUNDAMENTAL CONCEPT OF OXIDATION AND REDUCTION REACTION

Oxidation and reduction reactions are two processes which usually occur simultaneously. The
term redox is used by chemist as an abbreviation for the reactions and it involves not only the
addition and removal of hydrogen and oxygen, but has been extended to include all electron-
transfer processes. There definitions can be done under four headings.
9.1.1. IN TERM OF ADDITION AND REMOVAL OF OXYGEN
Oxidation is the addition of oxygen while reduction is the removal of oxygen.
i. ZnO + C Zn + CO
Zinc is reduced while carbon is oxidized
ii. CuO + CO Cu + CO2
CuO reduced while carbon II oxide is oxidized.

9.1.2. In terms of addition and removal of hydrogen

Oxidation is the removal of hydrogen while reduction is the addition of hydrogen
i. 4HCI + O2 2H2O + 2CI2
Chlorine is oxidized while oxygen is reduced
ii. H2S + CI2 2HCI + S
Sulphur is oxidized while chlorine is reduced

9.1.3. In terms of electron transfer

Oxidation is the loss of electrons while reduction is the gain of electrons.

2FeCI2 + CI2 2FeCl3

Iron (II) is oxidized while chlorine is reduced. The two half reaction can be written thus:
2Fe2+ - 2e- 2Fe3+ (oxidized)
- -
CI2 + 2e 2Cl (reduced)

9.1.4. In terms of change in oxidation number

Oxidation is the increase in oxidation number while reduction is the decrease in
oxidation number. A substance is oxidized if its oxidation number increases from left to right
while decrease in the oxidation number of a substance from left to right is reduction.

2C + 2HNO3 2CO+ H2O + 2NO2

Here, the oxidation number of C = O on the left and on the right it became C = 2+.
Therefore carbon has being oxidized.
In summary, oxidation is:
1. Addition of Oxygen
2. Removal of hydrogen
3. loss of electron
4. increase in oxidation number

91
While reduction is:
1. Removal of Oxygen
2. Addition of hydrogen
3. gain of electrons
4. decrease in oxidation number

9.2 OXIDISING AND REDUCING AGENTS

An oxidizing agent is a substance which brings about oxidation and its reduced in the cause of a
redox reaction.
Also a reducing agent is a substance which brings about reduction and it‟s oxidized in the cause
of a redox reaction. Illustration;

(i) CuO + CO Cu + CO2

Here copper has been reduced; therefore copper is the oxidizing agent while
carbon that has been oxidized is the reducing agent.

(ii) CuSO4 + Zn ZnSO4 + Cu

Here copper which is reduced is the oxidizing agent while zinc is oxidized hence
the reducing agent.

CuSO4 + Zn ZnSO4 + Cu
0 o
Cu2+ + Zn  Cu  Zn 2
reduced Oxidised
( Oxidi sin g Agent ) (Re ducing Agent )

9.3 TESTS FOR OXIDING AGENTS

1. Most oxidizing agent give off iodine from acidified potassium iodide solution, forming a
red-brown solution which turns dark-blue upon the addition of starch
2. Bubbling sulphur (IV) oxide through an aqueous solution of the substance will give
tetraoxosulphate (VI) ion.

9.4 TESTS FOR REDUCING AGENTS

1. Reducing agents decolorize the deep purple colour of acidified potassium
tetraoxomanganate (VII) (KMnO4)
2. Reducing agents produce a green solution upon warming with an orange solution of
acidified dipotassiumhepta-oxochromate (VI) (K2Cr2O7)

9.5 OXIDATION NUMBER

Oxidation numbers arecharge assigned to element in the free or combined states according to
some set rules. Oxidation number can also be known as oxidation state.

9.5.1 RULES FOR DETERMING OXIDATION NUMBER

1. The oxidation number of atoms of elements in an uncombined state is zero.

2. The oxidation number of a monoatomic ion is equal to the charge on the ion.

92
 3. The sum of all the oxidation numbers of atoms in a molecule (or a polyatomic ion) is
the charge on the particle.

4. In many compounds of oxygen, the oxidation number of oxygen is -2. But in

peroxides it is -1 and when oxygen is combined with fluorine (e.g. OF2), the
oxidation number of oxygen is +2

5. In many compound of Hydrogen, the oxidation number of hydrogen is + 1 except in

metal hydride where hydrogen has an oxidation number of -1

6. Halogens have a negative oxidation number but when they combine with oxygen e.g.
in oxide, oxoacids and oxoanions, they have a positive oxidation number

Example 9.1
Calculate the oxidation states of chlorine in
(a) HOCI (b) HClO3(c) KClO3

Solutions
(a)
Because the molecule is not carrying any charge, then the sum of all its oxidation numbers will
be equal to zero:-
+1-2+x=0
Making x subject we get
x = +2 -1
x = + 1 : - The oxidation number of chlorine is + 1.

(b) H=1
Cl = x
0=-6
Because it is triatomic we multiply the oxidation number of one oxygen atom (-2) by 3 to get -6
+1 + X -6 = 0
x = +6 -1
x = +5

(c) K=1
CI= x, 0=-6
1 + x -6 =
0 x = +6-1
x = +5

Example 9.2
Find the oxidation number of chromium atom in potassium heptaoxodicromate (VI) K2Cr2O7

93
K=1 x 2 = 2
Cr = xX 2 = 2x
0 = -2 x7 = -14

2 + 2x - 14 = 0
2x =+ 14-2
2x = +12
x = + 12
2
x = +6
Cr = +6

9.6 BALANCING OF REDOX EQUATION

9.6.1 By ion-electron or half reaction method

This method is a limited method as it is appliedonly in balancing redox reactions taking
place in aqueous solution, involving complete transfer of electrons. This method involves the
following steps;
i. Identify the oxidizing agent and the reducing agents
ii. Write half equation for the reaction
iii. In acid and neutral solutions, balance first for oxygen and next for hydrogen as follows
(a) Balance for every excess oxygen on one side, by adding water on the other side
and 2H+ on the same side.
(b) In alkaline medium, balance for every excess oxygen on one side by adding
2OH- on the other side. And one H2O on the same side and vice versa. If both
H and O are in excess on the same side, add OH- to the other side for each pair
of excess H and O
iv. Balance each half reaction for charge.
vi. Cross multiply with the number of charges and cancel out as necessary (equalize the
electrons).
vii. Add the two half equations, so that the electrons cancel out as well as other terms.

viii. Finally, insert necessary coefficients for the oxidizing and reducing agent according to the
law of conservation of mass

Example 9.3
Balance the redox equation
MnO4- + Fe2+ Mn2++ Fe3+
7
MnO4   Mn 2 (reduced)
( Oxidizing Agent )

Fe 2  Fe 3 (oxidized)
(Re ducing agent )

94
MnO4- + 8H+ Mn2+ + 4H2O

MnO4- + 8H+ + 5e Mn2+ + 4H2O

Fe2+ Fe3++ e-

Cross multiply with the number of charges and cancel out as necessary (equalize the electrons)

MnO4-+ 8H+ + 5e- Mn2+ + 4H2O

5Fe2+ 5Fe3+ + 5e-

Sum up

MnO4- + 8H+ + 5Fe2+ Mn2+ + 4H2O + 5Fe3+

Example 9.4

Balance the following equation using the half reaction method.

Reaction in acid medium

BiO3- + Mn2+ Bi3+ + MnO4-


BiO 3 Bi3+ (reduced)
(OA)

7
2 
Mn Mno 4 (oxidized)
( RA)


BiO 3 + 6H+ Bi3+ + 3H2O
(OA)

BiO 3 + 6H+ + 2e- Bi3+ + 3H2O
(OA)

Mn2+ + 4H2O MnO 4 + 8H

+

Mn2+ + 4H2O MnO 4 + 8H + 5e

+ -

16  7

5BiO  3OH 3  10e   5Bi 3  15 H 2O
2Mn 2 8H 2O  2MnO4  16H   10e 

5BiO3  2Mn 2  14H   5Bi 3  2MnO4  7 H 2O

Example 9.5
Balance the redox equation using half –reaction method
MnO4  Fe 2  MnO2  Fe 3

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Reaction in alkaline Medium

Solution
7 4
Mn O4  MnO 2 (reduced)
( OA)
2
Fe  Fe 3 (oxidized)
( RA)

MnO4  2 H 2 O  MnO2  4OH 

MnO4  2 H 2 O  3e   MnO2  4OH 
Fe 2  Fe 3  3e 
MnO4  2H 2O  3e   MnO2  4OH 
3Fe 2  3Fe 3  3e 
MnO4  3Fe 3  2 H 2O  MnO2  3Fe 3  4OH 

Example 11.11
Balance the redox equation in alkaline medium using the half-reaction method.
MnO4  C2O42   Mn 2   CO2
MnO4  C2O42   Mn 2   2CO2
7
MnO4  Mn 2  (reduced)
( OA )

6 8
2
C 2 O4  2 CO 2 (Oxidation)

MnO4  4 H 2O  Mn 2   8OH ( BFO )

  2 
MnO  4 H 2O  5e  Mn  8OH
4 ( BFC )
2 
C 2 O4   5CO2  2e
2MnO4  8H 2O  10e   2Mn 2   16OH 
2
5C2O4  10CO2  10e 
2
2MnO4  5C2O4  8H 2O 2Mn2 10CO2 16OH 

9.6.2 OXIDATION NUMBER METHOD

Not all redox reaction occurs in aqueous solution and a complete transfer of electrons is
always the casethus, to accommodate for this a wider balancing method is required.
The method is based on the fact that the partial or complete gain of electrons by the
oxidizing agent must be equal to the partial or complete loss of electrons by the reducing
agent. This method entails the following steps
I. Determine the oxidation number for every element in the equation. Record new
oxidation number below affected element. Indicate all increases and decreases in
oxidation number. Disregard signs

96
 +7
MnO4
-
Fe
2+
MnO4
-
+
+4
Fe
3+

+2 +3

+7 +4
increase of 1

Decrease of 3

Ii Cross multiply each half equation by their respective change in oxidation state. To
do this, multiply the Mn- half equations by 1 while the Fe half equation by 3.
MnO4  3Fe 2  MnO2  3Fe 3

iii. Balance for oxygen by adding water to every side short of oxygen

MnO4  3Fe 2  MnO2  3Fe 3  2 H 2 O

iv. Balance for hydrogen by adding hydrogen ion to any side short of hydrogen.

MnO4  3Fe 2  4 H   MnO2  3Fe 3  2 H 2 O

Example 9.6

Using the change in oxidation number method, balance the redox equation.

Cr2O72-+ H2S  Cr 3  S

+6 2-
-2 +3 3+
0
Cr 2O 7 + H2 S 2Cr + S

-2 0

+12 +6

increase of -2

Decrease of 6

97
 2Cr2 O7 2  6 H 2 S  4Cr 3  6 S
2Cr2 O7 2  6 H 2 S  4Cr 3  6 S  14H 2 O
2Cr2 O7 2  16H   6 H 2 S  4Cr 3  6 S 14H 2 O

Example 9.7

Balance the redox equation using the oxidation number method

Solution:
1 5 2 1 2 5 2
HN O 3  CU 2 O  CU ( N O3 ) 2  NO  H 2O

+5 +1 +2 +2
HNO3 CU 2O NO + 2CU(NO3) 2 + H2O

+2 +2 +3
+4

2 HNO3  3CU 2O  6CU ( NO3 ) 2  2 NO  H 2O

14HNO3  3CU 2O  6CU ( NO3 ) 2  2 NO  H 2O
14HNO3  3CU 2O  6CU ( NO3 ) 2  2 NO  7 H 2O

PRACTICE QUESTIONS

1. What is the oxidation number of (a) Aluminium in AI2O3 (b) Bromine in NaBr (c)
Sulphur in Na2S2O3 (d) Hydrogen in NH3 (e) Magnesium in KMnO4 (f) Chromium in
K2CrO4
2. Balance the redox equation, using the half-reaction method and assume that the reaction
takes places in an acidic medium.

Ag + NO 3  Ag   NO

3. Iron (iii) chloride reacted with zinc to yield Zinc (ii) chloride and pure iron metal.
Balance the redox equation assuming that the reaction occurred in an alkaline medium:
FeCl3 + Zn  ZnCl 2  Fe

4. Use the oxidation number method to balance the following redox equation

98
 (a) Cu  HNO3  Cu ( NO3 ) 2  H 2 O  NO
(b) Ag  NO3  Ag   NO

(c) MnO4  H 2 C 2 O4  Mn2  CO2

8. Balance the redox equation

Zn + HNO3  Zn(NO3)2 + NO2 + H2O

9. Balance the redox equation using the oxidation number method

(a) Zn  HNO3  Zn( NO3 ) 2  NH 4 NO3

b KMnO4  HCl  KCl  MnCl2  H 2O  Cl 2

99
 CHAPTER 10
CHEMICAL EQUILIBRIUM

10.1 EQUILIBRIUM
Equilibrium can be defined as a state when two opposing reactions are equal. Equilibrium is a
state of a system where there is no observable change in the properties of the system with regards
to time. There are two types of equilibrium namely:

10.1.1 STATIC EQUILIBRIUM

In this type of equilibrium, there is a total standstill of the two opposing reactions. An example is
when two kids are balanced on a sea-saw. At the point of balance, the kids and the sea-saw are in
a point of total stand still

10.1.2 DYNAMIC EQUILIBRIUM

An example of this type of equilibrium is a boy running up an escalator, and the escalator is
descending at the same rate at which the boy is ascending. When these two opposing processes
(i.e. the boy ascending and the escalator descending) occur at the same time and rate there will
be no observable change in the properties of the system.

Generally, dynamic equilibrium involving physical change is called physical equilibrium e.g.
when liquid water and solid water (ice) exist together. Also, dynamic equilibrium involving
chemical change is called the chemical equilibrium.

10.2 CHARACTERISTICS OF DYNAMIC EQUILIBRIUM

10.2.1 Constant macroscopic properties: That means that there is no overall large scale
change. As the two opposing processes are occurring at the same time and rate, no net change is
observed. The system seems to have come to rest to an external observer.

10.2.2 Continuing microscopic process: This means at equilibrium, molecular scale (very small
scale) processes continue, although at a balanced rate but cannot be measured by external
observer.

10.2.3 Equilibrium is reached only in a closed system: Considering the production of carbon
dioxide (CO2) by the decomposition of calcium trioxocarbonate (IV) (CaCO3). At equilibrium,
CaCO3 will be decomposing into CO2 and calcium (II) oxide (CaO) while the CO2 and CaO
produced will be reacting together again at the same time to form CaCO3.

CaCO3(S) CaO(S) + CO3(S)

100
When this reaction takes place in an open system. It is obvious that as the CaCO decomposes to
form CaO and CO2, the CO2 will be lost into the surrounding and thus there will be no CO2 to
react with the CaO to give the original CaCO3. Therefore, equilibrium will not be reached. But in
a closed system, either reaction can take place since there is no escape of any substance.

10.2.4 Equilibrium is attained from either direction: Again considering the above reaction, as
CaCO3 decomposes, CaO and CO2 is formed. Also CaO then combines with CO2 to produce
CaCO3. As the CaCO3 is decomposing, CaO and CO2 are combining at the same time and rate to
form CaCO3. Therefore, equilibrium is reached from the initial reaction and the final reaction.

10.2.5 None of the component in an equilibrium system is ever fully consumed: For the
forward and the backward reaction to take place at the same time and rate, the reactants and
products must be present in the system at all times.

10.3 EQUILIBRIUM IN REVERSIBLE REACTION

A reversible reaction is one that proceeds in both directions under suitable conditions. The two
direction under which a reversible reaction can proceed are called the forward and the backward
direction.

A reversible reaction is represented by two half arrows ( ). The arrow represents the forward
reaction while represents the backward reaction.

A+B C+D
Reactants Products

10.4 EQUILIBRIUM CONSTANT

Equilibrium constant is the constantrelationship that exists between concentrations of reactants

and products in a reversible reaction.It is explained by the law of mass action which states that at
constant temperatures the rate of a reaction is directly proportional to the active masses of each
of the reactants. The concentration of the reactants and products can also be used in place of the
active masses.

Considering the reaction;

aA + bB ............... .................cC + dD

Here a(moles) of A reacts with b(moles) of B to produce c(moles) of C and d(moles) of D. r1 and
r2 represents the rate of forward and backward reaction respectively. At a constant temperature,
the expression for the law of mass action is given by:

101
 r1 [A]a [B]b (Equation 10.1) for the forward reaction

r2 [C]c [D]d (Equation 10.2) for the backward reaction

r1 = K1 [A]a [B]b (10.3)

r2 = K2 [C]c [D]d (10.4)

Where K1 and K2 = velocity constant for the forward and backward reactions respectively. At
equilibrium, the rate of the forward reaction is equal to the rate of the backward reaction.
Therefore equation (10.3) is equal to equation (10.4).

r1 = r2
K1[A]a [B]b = K2[C]c [D]d

Rearranging so as to bring the constants on the same side, we get: =

It should be noted that in the mass action expression, the concentration of the products must
appear as the numerator while the concentration of the reactant as the denominator.

= K = equilibrium constant

Therefore, at constant temperature, the expression of the equilibrium constant is given by:

K= Equation10.5

The expression is also called the Equilibrium law. This law tells us that at constant temperature
regardless of the concentration of the reactants and products, the equilibrium constant is the ratio
of the rate of the forward reaction to the rate of the reversed reaction. This ratio is a constant for
that reaction. An example, is the reversible reaction at equilibrium between hydrogen and iodine
to produce hydrogen iodide at a temperature of 458°C

I2(g) + H2(g) 2HI(g)

We have:

Initial conc. in md/dm3 Equilibrium conc. in mol/dm3

S/N
[H2] [I2] [H1] [H2] [I2] [H1] Kc
-2 -2 -2 -2 -2
1. 2.40 x 10 1.68 x 10 0 0.92 x 10 0.21 x 10 3.00 x 10 46.58
2. 2.44 x 10-2 1.98 x 10-2 0 0.77 x 10-2 0.31 x 10-2 3.34 x 10-2 46.13
3. 2.46 x 10-2 1.76 x 10-2 0 0.92 x 10-2 0.22 x 10-2 3.08 x 10-2 46.87
4. 0 0 3.04 x 10-2 0.35 x 10-2 0.35 x 10-2 2.35 x 10-2 46.40

102
From this results, it is observed that within the limits of experimental errors, and regardless of
what the initial concentrations of hydrogen, iodine or hydrogen iodine were, at equilibrium when
their concentration are substituted into the mass action expression, the result will always be
constant.

The equilibrium constant Kc gives very useful information about the reaction. It tells how far a
reaction proceed before equilibrium is reached.
1. If Kc is large, it indicates that the forward reaction goes almost to completion before
equilibrium is reached. And at equilibrium, the product will be greater than the reactant.
2. If Kc = l, it indicates that the concentration of the products and reactants are the same
when equilibrium is reached.
3. If Kc is lesser than 1, it indicates that the forward reaction does not go far before
equilibrium, is reached. And at equilibrium, the reactant will be greater than the product.

The equilibrium constant is not affected by changes in concentration, pressure and catalyst. But a
change in temperature affects the equilibrium constant. At higher temperature, K values
increases and the product of that particular reaction. Changes in concentration and pressure will
not affect the value of the equilibrium constant because the reaction will automatically adjust
itself to attain equilibrium again to give the same Kc value. Also, the presence of a catalyst will
not affect the value of the equilibrium constant, it will only lower the activation energy so that
the rate of the reaction becomes faster, but still the same K value is obtained.

Equilibrium constant does not have a definite unit. The unit depends on the unit on the numerator
and the denominator of the equilibrium law expression. Kc will have no unit when the reaction
involves equal number of particles „in the products (numerator) and the reactant (denominator)
sides, e.g.

I2(g) + H2(g) 2HI(g)

( )
Kc = units =( )( )

= no units

For reactions where the mass-action expression gives unequal particles in the numerator and
denominator, K will have a unit e.g.
( )
Kc = units =( )( )

=( = mol-2 dm6
)

10.5 EQUILIBRIUM CONSTANTS INVOLVING GASES

103
So far we have expressed equilibrium constant with Kc. For reaction involving gases, it is more
convenient to express equilibrium constant in terms of the partial pressure of the gases. This is
because the partial pressure of gases is proportional to its mole fraction. Therefore, the
equilibrium expression of our earlier example;

H2(g) + H2(g) 2HI(g)

Becomes: Kp =

8.6 THE RELATIONSHIP BF TWEEN Kc AND Kp

Using the ideal gas equation:

Pv = Nrt ……………………………….. (Equation 10.6)

Rearranging equation (10.6) we get:

P = RT ……………………………….. (Equation 10.7)
Where:
P = Pressure of the gas in atmosphere

R = Gas Constant
T = Temperature in Kelvin
Number of moles of the gas per volume(is the effective concentration of the gas)
= [gas]
Equation (10.7) can be written thus:
P = [gas] RT …………………………… (Equation 10.8)

At constant temperature, the pressure of the gas will be directly proportional to the concentration
of the gas. Thus,

P [gas]

Applying this in an equilibrium expression

N2O4(g) 2NO2(g)
We get
( )
Kc = ………………………….. (10.9)
( )

( )
Kp = ………………………….. (10.10)
( )

From equation (8.8) P = [gas] RT. Substituting (10.8) in (10.10) we get:

( ) ( )
Kp = = ……………….. (10.11)

104
 ( )
Recall that from equation (10.9) that Kc = Kc =
( )

Therefore substituting (10.9) in (10.11) we get

KP = Kc RT ………………............. Equation 10.12

Note: This is not always the case.

Let us consider another example:

N2(g) + 3H2(g) 2NH3(g)

PV = nRT ………………………………..... (10.13)

P = RT ………………………………… (10.14)

P = [gas]RT ……………………………... (10.15)

( )
Kc = …………………. (10.16)
( ) ( )

( ( ))
Kc = Kp = ( ……….. (10.17)
( ) )( ( ))

( )
Kp = ………........... (10.18)
( )( )

( )
Kp = ………………… (10.19)
( ) ( ) ( )

Kp = ………………….... (10.20)
( ) ( ) ( )

Substituting (10.16) in (10.20) we get

KP = KC (RT)2 ……………………………. (10.21)

The relationship between Kp and Kc can be generalized thus

KP = KC( )

Where;

= (No. of moles on product side) – (No. of moles on reactant side)

Note: In this calculation, temperature must be expressed in Kelvin; pressure must be expressed
in pascal.

105
Celsius temperature + 273 = Kelvin temperature 1 atm 105 Pascal

10.7 HETEROGENEOUS EQUILIBRIA

So far, we have being talking about a single phase equilibria (homogeneous equilibria). An
equilibria involving more than one phase is called heterogeneous

equilibria.

An example is CaCO3(S) CaO(S) + CO2(g)

Here, CaCO3 and CaO are in a solid phase While CO2 is in a gaseous phase.

The equilibrium expression for the reaction can be written thus:

( ) ( )
KC =
( )

Since the ratio of moles to volume is constant for solid, then their concentration is constant.
Therefore the equation can be simplified by writing the equilibrium expression „in such a way
that the concentration of solid and liquid (note, not aqueous) is removed in the equilibrium
expression. Therefore, our equation becomes:

KC = [CO2(g)] OR KP = PCO(g)

Also for CaO(s) + SO2(g) CaSO3(s)

We have:

KC = OR
( )

KP =
( )

Examples 10.1:
PCl5(g) PCl3(g) + Cl2(g)

If the equilibrium concentrations of the PCI5 and PCl3; are 0.015 mol/dm3 and 0.78 mol/dm3
respectively,what is the concentration of Cl2 if Keq of the system is 35 at a certain temperature?

Keq =

35 =

[Cl2] = = 0.67mol/dm3

106
Example 10.2:

At equilibrium a 1.0L vessel contains 20mol of H2, 18mol of CO2, 12.0mol of water (H2O) and
5.9mol of CO at 427°C. What is the value of K at this temperature?

CO2(g) + H2(g) CO(g) + H2O(g)

Keq =

Keq = = 0.196 = 0.2

Example 10.3:

At equilibrium, the quantities of the substances present in a 20dm3 container are: 1.70 mole of
COCl2, 0.76mol of CO and 1.50 mole of Cl2 for the temperature at which equilibrium is reached.
What is Keq for the reaction?

COC12(g) CO(g) + Cl2(g)

[COCl2] = = 0.085

[CO] = = 0.038

[Cl2] = = 0.075

Keq = = x 0.075 = 0.0335mol/dm2

Example 10.4:

When 1.0mol of N2O4 is placed into a 5.0dm3 container at 100 C, part of it decomposed to form
NO2. At equilibrium, when the temperature is 100°C. 1.0mol of NO2 is present. Calculate K for
the reaction at 100°C. The balanced equation for the reaction is:

N2O4 2NO2

N2O4 NO2
At start 1.0mol 0

= = 0.2mol/dm3

At equilibrium 0.1 1.0mol

= = 0.2mol/dm3

107
From the equation, 1 mol N2O2 decomposes to give 2mol of NO2. Therefore 0.1 was
decomposed to give 0.2mol NO2 and so 0.1 N2O4 will be left at equilibrium.
( )
Keq = = = 0.40

Example 10.5:
A 1.00mol sample of HI(g) is heated to 510°C in a sealed flask with a volume of 1.00dm3. At
equilibrium, 0.14mol of each of the product, H2(g) and I2(g) is present.
(a) Calculate the number of moles of HI that are present at equilibrium.
(b) Write the equilibrium expression for the reaction.
(c) Calculate Keq

2HI I2 +H2

HI I2 H2
Moles before reaction 1.0 0 0

Moles at equilibrium x 0.14 0.14

From the equation, 2 moles of HI decomposes to give 1 mole of I2 and H2. Therefore at
equilibrium, 0.28 HI is used up and 0.72 HI will be left at equilibrium.

HI left at equilibrium = l – 0.28 = 0.72 moles

Keq =

Keq =

Keq = = 0.378 or 3.73 x 10-2

Example 8.6:

Hydrogen and iodine react at 426°C according to:

H2(g) + I2(g) 2HI(g)

If 1.00mol of H2 and 1.00mol, I2 are placed in a 1.00 litre vessel and allowed to react, what
weight of HI will be present at equilibrium. Keq= 55.3

H2 I 2HI
At start 1 1 0
At equilibrium 1–x 1–x 2x

108
 ( )
Keq = ( )

( )
55.3 = ( )

√ =

7.4 (1 – x) =

7.4 (1 – x) = 2x

7.4 – 74x = 2x

7.4 = 2x + 7.4x

7.4 = 9.4x

X = = 0.79mol

Concentration of HI = 2x

= 2 x 0.79

= 1.6mole

Reacting mass = Molar mass x No. of mole

= 126.9 x 1.6

= 203.04g

10.8 LECHATELIER’S PRINCIPLE

Lechatelier's Principle states that if an external constraint such as change in temperature, pressure
or concentration is imposed on a chemical system in equilibrium, the equilibrium position will
shift so as to annul the constraint. This principle is used to determine the optimum operating
condition for chemical processes in industries.

10.8.1 EFFECT OF TEMPERATURE ON EQUILIBRIUM

The effect of temperature on equilibrium of reversible reaction depends on the value of H

(enthalpy change) of the reaction. A positive value for H implies that the reaction is
endothermic in the forward reaction i.e. heat is absorbed in the forward reaction and the product
tend to be cooler, while the backward is exothermic. A negative value of H implies that the

109
reaction is exothermic in the forward reaction i.e. heat is evolved, or liberated in the forward
reaction and the product will tend to be hotter, while the backward is endothermic.

hot cold
A+B C H = + Ve
ExothermicEndothermic

cold hot
A+B C H = - Ve
EndothermicExothermic

According to Lechatechier's principle, a change in temperature will cause the equilibrium

position to shift so as to annul the effect of the change in temperature. Therefore in an
endothermic reaction increase in temperature will shift the equilibrium to the forward reaction.
While decrease in temperature, will favour the backward reaction. In the same way, in an
exothermic reaction, increase in temperature will shift the equilibrium position to the backward
reaction and decrease in temperature will favour the forward reaction.

Examples 10.6

1. N2(g) + O2(g) 2NO(g) H = 90.4kj/mol-1

This is an endothermic reaction. An increase in the temperature will shift the equilibrium to the
forward reaction (right) giving a higher value of K meaning a greater yield of product. While a
decrease will favour the backward reaction (left), giving a lower value of K which means a
greater yield of reactant.

2. 2SO2(g) + O2(g) 2SO3(g) H= -395.7kj/mol-1

This is an exothermic reaction. An increase in temperature will shift the equilibrium to the left
(backward reaction), while a decrease in temperature will shift the equilibrium position to the
right.

10.8.2 EFFECT OF PRESSURE ON EQUILIBRIUM

For a change in pressure to affect a chemical equilibrium, the following must be in place;
1. At least one of the reactants or products in the reversible reaction must be gaseous.
2. The total moles of gaseous molecules in the forward and reversed reaction must not be the
same e.g.

N2(g) + 3H2(g) 2NH3(g)

Backward reaction has 1 mole N2 and 3 moles H2 making a total of 4 moles, while forward
reaction has 2 moles NH3.

110
According to Lechatechier's principle, if a high pressure is imposed on a system in equilibrium,
the equilibrium will shift to the position of low pressure. Also if low pressure is imposed on an
equilibrium system, the equilibrium position will shift to the position of higher pressure.

It should be noted however, that the position of high pressure is that with the greater volume or
greater number of moles. The position of low pressure is that with less volume or lesser numbers
of moles.

In the reaction above, increase in pressure will favour the forward reaction while decrease in
pressure will favour the backward reaction. In both cases the equilibrium constant K remains
unchanged.

10.8.3 EFFECT OF CONCENTRATION ON EQUILIBRIUM

In an equilibrium mixture, there is a balance between the concentrations of the reactants and the
products i.e. these concentrations are in a definite ratio which depends on the condition of the
reaction. If more reactants are introduced into the equilibrium system the equilibrium will shift to
the right favouring the forward reaction. This results in a proportional increase in the
concentration of the products and so the equilibrium constant remains constant. Another way of
increasing the amount of products formed is by continually removing the products from the
system. Again in order to remove the constraint, the equilibrium will shift to the right, favouring
the forward reaction.

Let us consider the reaction below:

3Fe(S) + 4H2O(g) Fe3O4(S) + 4H2(g)

If the concentration of a reactant or product is changed, the equilibrium position shifts to

annul the change. Increase in the concentration of Iron will shift the equilibrium to the right and
a decrease in hydrogen concentration will also favour the forward reaction. But when Fe 3O4 is
increase or H2O is reduced, the backward reaction is favoured.

10.8.4 EFFECT OF CATALYST ON EQUILIBRIUM

Catalyst does not affect the position of equilibrium. It cannot be used to increase product
formation. However, catalyst is very important in chemical industry because they affect the time
taken for a reaction to reach equilibrium by lowering the activation energy for a positive catalyst
and increasing the activation energy for a negative catalyst.

111
PRACTICE QUESTION

1. Write down the equilibrium constant for each of the following reaction?
(a) CO(g) + 2H2(g) CH3OH(g)
(b) C2H4(g) + H2O(g) C2H5OH(g)
(c) 2Mg(g) + O2(g) 2MgO(g)
(d) C(s) + O2(g) CO2(g)
(e) H2(g) + CO2(g) H2O(g) + CO(g)
(f) CH3COOH(aq) CH3COO(aq) + H+(aq)
(g) NH4Cl(s) NH3(g) + HCl(g)
(h) Ce4+(aq) + Fe2+(aq) Ce3+(aq) + Fe3+(aq)
Use K or Kc depending on the states of the chemical.
2. At equilibrium at 1.0L vessel contains 20.0mol of H2, 18.0mol of CO2 of 12.0mo1 of H2O
and 5.9mol of CO at 427°C. What is the value of K at this temperature? Equation for the
reaction is:

CO2(g) + H2(g) CO(g) + H2O(g)

3. A reaction between gaseous sulphur dioxide (SO2) and Oxygen (O2) gas to produce
gaseous sulphur trioxide (SO3) takes place at 600°C. At that temperature, the concentration
of SO2 is found to be 1.50mol/L, the concentration of O2 is 1.25mol/L, and the
concentration of SO3, is 3.50mol/L. Using the balanced chemical equation, calculate the
equilibrium constant for the system.
4. For the reaction:
H2(g) + 12(g) 2HI(g) at 425°C.

Calculate [HI], given [H2 = [I2] = 4.79 x 10-4 mol/L and K = 54.3

5. What is the effect of increase in (i) temperature (ii) pressure and (iii) concentration on the
equilibrium reaction?

SO2(g) + O2(g) 2SO3(g) H = -395.7kj/mol-1

112
 CHAPTER 11
INTRODUCTION TO SOLUTION CHEMISTRY

11.1DEFINITION OF SOLUTION
A Solution is a homogeneous mixture of two or more substances in the same or different
physical phases, intimately mixed that it behaves like a single substancein many ways. The
substances forming the solution are called components of the solution. In solutions that consist of
two components,the component which is present in the higheramount is called the solvent while
the other component present in a lower amount is known as solute.With respect to the higher and
lower amount we mean presence by mass or by moles. Sometimes this becomes confusing when
dealing with substances with very close masses or moles. However, we will limit our discussion
to binary solutions withvery obvious larger and lower components.

11.2 CLASSIFICATION OF SOLUTIONS

Solution can be classified based on different criteria;

11.2.1PHYSICAL STATE OF SOLUTE AND SOLVENT

Table 10.1 Classified of solution based on physical state of solute and solvent

S/NO SOLUTE SOLVENT EXAMPLES

Solid Solution
1 Solid Solid Alloys
2 Liquid Solid Hydrated salts,
amalgam of Hg with
Na
3 Gas Solid Dissolved gases in
minerals
Liquid Solution
4 Solid Liquid Salt/sugar in water,
5 Liquid Liquid Ethanol in water
6 Gas Liquid Carbonated drinks,
O2 in air
Gaseous Solution
7 Solid Gas Iodine vapour in air
8 Liquid Gas Water vapour in air
9 Gas Gas Air , ( O2+ N2)
Solutions were water is used as the solvent is called aqueous solution and if not, the
solution is called non-aqueous solution.

11.2.2BASED ON THE AMOUNT OF SOLUTE DISSOLVED IN A SOLVENT

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a. Unsaturated solution: This is a solution that contains lower solute than the solvent can
accommodate at the given temperature. This means at that at a given temperature more solute
can be dissolved in the solvent.

b. Saturated solution: This solution has just enough solute that can be dissolved in the solvent
at that given temperature such that no solute can be dissolved further. Any further addition will
precipitate back the solute

c. Supersaturated solution:This solution contains more solute than can be dissolve in the
solvent at that particulartemperature.

One important concept of solutions is in defining how much solute is dissolved in a given
amount of solvent. This concept is called concentration. Various words are used to describe the
relative amounts of solute in a solution. Dilute describes a solution with very little solute, while
concentrateddescribes a solution with a lot of solute. One problem is that these terms are
qualitative (they describe only more or less) but not exactly how much.

Several units commonly used to express the concentrations of solution have been discussedin
chapter five of this text. Many concentration values varydue to the contraction/expansion of the
volume of solution with temperature. For example,Molarity varies with temperature such that
concentration of solutions with identical numbers of solute and solvent species can be different at
different temperatures. Therefore the more appropriate concentration units used for calculations
involving many colligative properties are mole-based whose values are not dependent on
temperature. Two such units are mole fraction and molality.

The mole fraction,X of a component A is the ratio of its molar amount to the total number of
moles of all solution components:

XA = = mole fraction of liquid A

Mole fraction has no unit being the ratio of properties with identical units (moles).

Molality is a concentration unit defined as the ratio of the numbers of moles of solute to the mass
of the solvent in kilograms:

m=

Since these units are computed using only masses and molar amounts, they do not vary with
temperature and, thus, are better suited for applications requiring temperature-independent
concentrations, including several colligative properties, as will be described in this chapter.

11.3 SOLUBILITY
Generally, only a certain maximum amount of solute can be dissolved in a given amount of
solvent at a particular temperature. This maximum amount is called the solubility of the solute. It

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is usually expressed in terms of the amount of solute that can dissolve in 100 g of the solvent at a
given temperature. These solubilities vary widely for different solutes. For example NaCl can
dissolve up to 31.6 g per 100 g of H2O, while AgCl can dissolve only 0.00019 g per 100 g of
H2O.The maximum amount of a solute that can be dissolved in a 100g of solvent at a given
temperature is termed as its solubility at that temperature. The solubility of a solute in a liquid
depends upon the following factors:

(i) Nature of the solute

(ii) Nature of the solvent
(iii) Temperature of the solution
(iv) Pressure (in case of gases)

11.4 RAOULT’S LAW

It states that the partial pressure exerted by any component of an ideal solution is proportional to
its mole fraction in the solution.

PA α XA ,PA = k XA
P°A = k
Therefore,PA = P°A XA
P°A, = vapour pressure of pure liquid

XA = = mole fraction of liquid A

In other words, the law can also be stated as; the partial pressure exerted by any component of an
ideal solution is equal to the vapor pressure of the pure component multiplied by its mole
fraction in the solution.

11.5 IDEAL SOLUTION

An ideal solution is one where the solvent – solvent (A-A) and the solute – solute (B-B)
interactions are similar to the solvent – solute (A - B) interactions. An ideal solution
obeys Raoult‟s law. That is the equilibrium partial pressure of the one of the component(say
solvent component A) is directly proportional to its mole fraction. That is a plot of PA against
XA gives a straight line graph.

Figure 10.1 A plot of the equilibrium partial pressure (PA)against mole fraction (XA)

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PA α XA ,PA = k XA

XA = = mole fraction of liquid A

The proportionality constant k = P°A, is the vapour pressure of pure liquid, hence
PA = P0XA Similarly,
PB =P0 XB
Therefore, Total pressure of the solution PT = PA + PB = P0XA + P0 XB
Three conditions must be satisfied before a solution can be termed ideal;

i. Obeys Raoult‟s law i.e. PA = P0XA , PB = P0 XB

ii. ΔHmix = 0 (ie no energy is evolved or absorbed)
iii. ΔVmix = 0(ie no expansion is contraction on mixing)

11.6 NON IDEAL SOLUTION (DEVIATION FROM RAOULT’S LAW)

Those solutions which show deviation from Raoult‟s law are called non-ideal solution. There
deviation from Raoults law can be positive or negative.
For such solutions,
ΔHmix ≠ 0
ΔVmix ≠ 0

11.6.1 Non-ideal solutions showing positive deviation: In such a case, the A – A or B – B

interactions are stronger than A – B interactions and the observed vapour pressure of each
component and the total vapour pressure are greater than that predicted by Raoults law. That is
the vapour pressure of component A or B is greater than the vapour pressure of the pure solvent
multiplied by the mole ratio. The solution will have more vapour than the solution.
PA >P0XA
PB >P0 XB

Figure 10.2 A Plot showing positive deviation from Raoult’s law

Examples of these type of solutions includes ethanol+ water, carbon disulphide(CS2) +

acetone, ethanol + cyclohexane

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11.6.2Non-ideal solution showing negative deviation In this case, the A – A or B – B
interactions are weaker than A – B interactions and the observed vapour pressure of each
component and the total vapour pressure are lower than that predicted by Raoult‟s law. That is
the vapour pressure of component A or B is lower than the vapour pressure of the pure solvent
multiplied by the mole ratio. The solution will be lower vapour than the solution.
PA <P0XA
PB <P0XB

Figure 11.3 A Plot showing negative deviation from Raoult’s law

Examples of these type of solutions includes methanol + acetone, acetone + chloroform

(CHCl3), H2O + HCl, H2O + HNO3, CHCl3 + CH3COCH3

11.8 COLLIGATIVE PROPERTIES

Colligative propertiesare properties that a solution exhibits which depend only on the number of
solute particles(or concentration of the solute) that is dissolved in the solvent and not on the
chemistry of the solute.These properties are;

i. Lowering of vapour pressure of the solvent

ii. Elevation of boiling point of the solvent
iii. Depression of freezing point of the solvent
iv. Osmotic pressure
Dissolving a solute in a solvent interferes with the activities of the solvent particles such that the
solution that is produced has different physical properties compared to the pure solvent alone.
This interference result in lowering of the vapour pressure, elevation of the boiling point and
depression of the freezing point. Since these properties are associated with the number of solute
particles in the solution, one can use them to obtain the molecular weight of the solute.

11.8.1Lowering of vapour pressure of the solvent: When a non- volatile solute such as sugar
or common salt is dissolved in a solvent the resultingsolution will have a lower vapour pressure

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than the pure solvent. The amount of lowering is dependent on the fraction of solute particles in
the solution, and the change is usually not much at all as long as the solute itself does not have a
significant vapour pressure (nor has a vapor pressure of zero). This colligative property is called
vapour pressure depression (or lowering).The vapour pressure of a solvent in a solution is always
lower than the vapor pressure of the pure solvent. The vapor pressure lowering is directly
proportional to the mole fraction of the solute.

Psoln α χsolv

Psoln=χsolvPosolv

Where
Psoln = the vapour pressure of the solution
χsolv = the mole fraction of the solvent particles
Posolv = the vapour pressure of the pure solvent at that temperature

This equation is also known as Raoult‟s law. The assumption here is that solute particles take
positions at the surface in place of solvent particles, so not as many solvent particles can be
evaporated.
χsolv + χsolute=1
where, χsolute = mole fraction of the solvent or solute.

Figure 11.4 A demonstration oflowering of vapour pressure experiment

The change in vapor pressure (ΔP) can be expressed as

ΔP=Psoln−Posolv= χsolv Posolv−Posolv

or

ΔP=(χsolv−1)Posolv=χsolutePosolv

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Example 11.1: Calculate the vapor pressure of a solution made by dissolving 47.0 g glucose,
C6H12O6, in 545 g of water. The vapor pressure of pure water is 47.1 torr at 37°C. (Molar
masses, water = 18 g/mol , glucose = 180.2 g/mol )

Solution

We will use Raoult's Law,Psoln = χsolv Posolv

χsolv=

Solvent = 545g water

Solute = 47g glucose

Mole ratio of solvent = χsolv =

χsolv =

nwater=

nglucose=

χsolv =

Psoln=0.99×47.1=46.63torrnot much of a change at all.

11.8.2Elevation of boiling point of the solvent: A liquid boils at a temperature when its vapour
pressure is equal to the external pressure on the surface of the liquid. Boiling-point elevation
describes the process whereby the boiling point of a liquid (a solvent) is increased by the
addition of a non-volatile solute, thus the solution has a higher boiling point than its pure
solvent.The solute particles interfere with the solvent particles in a manner that solution boil at a
higher temperature compared to the pure solvent. Usually, the boiling point of water increases by
0.5120C whenever one mole of any non-electrolyte is dissolved in 1kilogram of water. And the
boiling point of the pure solvent is directly proportional to the molal concentration of the solute.

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The change in boiling point of dilute solution ΔTb, from that of the pure solvent is given by the
expression.

ΔTb = mKb

Here, m = molality of the solution

Kb = molal boiling point elevation constant. This value is a characteristic of the solvent and it
varies with different solvent. Some boiling point elevation constants (as well as boiling point
temperatures) are listed in Table11.2

Table 11.2 Boiling Points, freezing points, molal boiling point elevation and freezing point
depression constants for various solvents (Liquids)

Liquid Boiling Point Kb (°c/m) Freezing Kf (°c/m)

(°C) Point (°C)
HC2H3O2 117.90 3.07 16.6 3.9
C6H6 80.10 2.53 5.48 5.12
CCl4 76.8 4.95
H2O 100.00 0.512 0.00 1.86
Chloroform 61.26 3.63 -63.5 4.68
nitrobenzene 210.9 5.24 5.69 8.1

11.8.3 Depression of freezing point of the solvent: The freezing point of a liquid (i.e. a pure
solvent or a solution) is the temperature at which its solid and liquid are at equilibrium so that
both have equal vapour pressure. Here the present ofsolute particles interfere with solvent
particles such that the ability of the solvent particlesto effectivelyform solid (ice) is hampered
and solidification(freezing) then occursat a lower temperature. This is called freezing point
depression.This explains why sea water with its large salt content freezes at lower temperatures
than pure water.The equation to calculate the change in the freezing point for a solution is similar
to the equation for the boiling point elevation:

ΔTf = mKf

Where,
m= molality of the solution
Kf = thefreezing point depression constant, which is also a characteristic of the solvent.

Although freezing-point depression is similar to boiling point elevation but the magnitude of the
freezing point depression is larger than the boiling point elevation for the same solvent and the
same concentration of a solute. Because of these two phenomena, the liquid range of a solvent is
increased in the presence of a solute.

Example 11.2: Calculate the boiling point elevation of water when 1.20g of glycerin C3H8O3 is
dissolved in 47.8g of water (Kb for water = 0.501C/m, Atomic masses, C = 12 g/mol, O = 16
g/mol, H = 1 g/mol )

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 Solution

Molar concentration of glycerin Mglycerin=

Mglycerine

Molal concentration of glycerin mglycerin =

ΔTb = mKb

0.5010C/m = 0.1170C

Example 11.3:Calculate the boiling and freezing point of a 0.8m aqueous solution of glucose
(Kb = 0.510C/ m, Kf = 1.860C/m)

Solution

0.5010C/m

0.410C

Tb = 1000C + 0.410C = 100 .410C

1.860C/m

.490C

Tf= 00C - 1.490C = -1 .490C

11.8.4Exhibition of osmotic pressure: Osmosis is the flow of solvent molecules to the region of
solute molecules through semi- permeable membrane. The semi-permeable membrane stops the
flow of solute molecules only. If a solution and its pure solvent are placed side by side in
between a semi-permeable membrane, more solvent molecules would flow out from the pure
solvent into the solution than vice versa. That flow of solvent from the pure solvent side makes
the volume of the solution to rise while the volume of the solvent drops. When the height
difference between the two sides becomes large enough, the net flow through the membrane
ceases due to the extra pressure exerted by the excess height of the solution chamber and
equilibrium is thereby reached. The pressure difference between the two regions at equilibrium is
called the osmotic pressure of the solution. Figure 11.4shows a typical setup for measuring the
osmotic pressure of a solution.

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For dilute solutions, osmotic pressure is proportional to the molar concentration M of the solute
ΠαM
Π = MRT

Where;
Π = osmotic pressure of a solution
M = molarity of the solution
R is the ideal gas law constant
T is the absolute temperature. This equation is reminiscent of the ideal gas law we considered in
our earlier chapter; Pv = nRT
Also, Π = RT
OR Πv = nRT

Example 11.4
What is the osmotic pressure of a 0.333 M solution of C6H12O6 at 25°C?
(R = 0.08206 L atm/mol K )

Solution

First we need to convert our temperature to kelvins:

T = 25 + 273 = 298 K

Now we can substitute into the equation for osmotic pressure:

Π = MRT

Π = 0.333M x 0.08206 L atm/mol Kx 298 K = 8.143atm

Example 11.5

What is the osmotic pressure of a 0.0522 M solution of C12H22O11 at 55°C?

Solution

First we need to convert our temperature to kelvins:

T = 55 + 273 = 328 K

Now we can substitute into the equation for osmotic pressure:

Π = MRT

Π = 0.0522M x 0.08206 L atm/mol Kx 328 K = 1.405atm

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PRACTICE QUESTION

1. If 115g of N2 are mixed with 145g of O2, what is the mole fraction of each
component?

2. If 34.5 g of NaCl are mixed with 65.5 g of H2O, what is the mole fraction of each
component?
3. A solution is made by mixing 43.9 g of C6H12C6 in 100.0 g of H2O. If the vapour
pressure of pure water is 26.5 torr at a particular temperature, what is the vapour
pressure of the solution at the same temperature?
4. At 300°C, the vapour pressure of Hg is 32.97 torr. What mass of Au would have
to be dissolved in 5.00 g of Hg to lower its vapour pressure to 25.00 torr?
5. If 123 g of C10H16O are dissolved in 355 g of C6H6, what is the boiling point of
this solution?
6. A solution of C2H2O4 in CH3COOH has a boiling point of 123.40°C. What is the
molality of the solution?
7. If 25.0 g of C6H12O6 are dissolved in 100.0 g of H2O, what is the freezing point of
this solution?
8. C8H17OH is a nonvolatile solid that dissolves in C6H12. If 7.22 g of C8H17OH is
dissolved in 45.3 g of C6H12, what is the freezing point of this solution?
9. If 25.0 g of C6H12O6 are dissolved in H2O to make 0.100 L of solution, what is the
osmotic pressure of this solution at 25°C?
10. At 298 K, what concentration of solution is needed to have an osmotic pressure of
1.00 atm?

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 CHAPTER 12
INTRODUCTION TO NUCLEAR REACTION AND RADIOACTIVITY

After the discovery of the cathode rays, many scientists became interested in the study of
different types of rays. Their researches led to the discovery of the radioactive rays. In 1846
Wilhelm Rontgen discovered that when cathode rays hit glass or metals new and very unusual
rays were emitted. These rays were highly energetic and could penetrate matter. Also, the rays
could darken covered photographic plates and they produced fluorescence in various substances.
However they were not deflected by magnetic and electric fields, suggesting that rays did not
consist of charged particles. Rontgen named the rays X- rays.

Soon after Rontgen discovery, Antoine Becquerel in 1896 while studying the fluorescent
properties of substances, accidentally discovered that certain compound containing Uranium
emitted radiation. The radiation could penetrate opaque materials like thick paper and thin metals
sheet after which it will also darken photographic plates. The rays also had properties similar to
X- ray by being highly energetic and not consisting of charged particles.

In 1898, Pierre and Marie Curie who were both Becquerel‟s students detected that thorium had
radioactive properties and that the level of radiation in a naturally occurring uranium ore (also
known as pitchblend), was quite higher than its uranium content. As a result of this observation,
they subjected the uranium ore to further analysis and two new radioactive elements – polonium
and radium were isolated. Radium was found to be several million times more radioactive than
the same mass of uranium.

Further studies later revealed that the phenomenon was different from ordinary chemical reaction
which involves electron transfer by atoms. This phenomenon involves changes in the atomic
nuclei (that is new elements were formed by radioactive radiation),therefore, Becquerel named
the phenomenon radioactivity. And elements which exhibit radioactivity were termed
radioactive. Thus, radioactivity can be defined as the spontaneous disintegration of a radioactive
element. It can also be defined as the emission of radiation from radioactive element.

RADIATIONS TYPES AND CHARACTERISTICS

Radioactive substances emits radiation spontaneously, independent of temperature and pressure.
The energy released during radioactive emission is known as nuclear energy which is about a
million times higher than the energy released during any chemical reaction. Radioactive
radiations share some similar properties with light such as having effect on photographic plate,
ionizing the gas through which the radiation passes and also causing flouresence in certain
substances such zinc sulphide. It also leave a track in a cloud chamber – this can used as a means
of identifying the type of radiation. Unlike light rays, however radioactive radiations can
penetrate opaque materials. Three major radiations are emitted by radioactive elements which
can be differentiated based on their behaviors in an electric field. They are:
i. Alpha rays
ii. Beta rays
iii. Gamma rays

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Alpha(α) – rays
The α -rays are fast moving streams of positively charged particles , with each particle having a
mass number of 4, an atomic number of 2 and 2 unit positive charge. That is each α – particle is a
helium nucleus and it is 8,000 times the mass of a beta particle. Because of their large mass and
their positive charge, the particles are attracted to a small extent towards the negative plate of an
electric field. The same large size of alpha particles gives them the highest ionizing power (that
is the greatest ability to damage tissue) and makes them less able to penetrate matter. As such
can be stopped or absorbed by a thin sheet of paper or an aluminum foil that is only 0.1mm thick.
And also the rays cannot be penetrated through the human skin. However, there is great danger
when the beta emission source gets inside someone. The rays can cause fluorescence in some
materials such as zinc sulphide. The emission of an α – particle result to the formation of a new
element having 4 mass number and 2 atomic number short from the original radioactive element.
examples are the emission of α – particle respectively from radium and polonium.
224 224 4
88Ra 88Ra + 2He

208 204 4
84Po 82Pb + 2He

Beta (β) –rays

Beta – rays are very fast moving streams of electrons with each particle having a mass number of
zero with atomic number of -1 and a charge of -1. They are deflected significantly toward the
positive plate of an electric field because they are negatively charged and much smaller than
alpha particles. Also because of their small size, they have much less ionizing power (less ability
to damage tissue) and much greater penetration power. The beta particles have penetrating range
of about 3m in air and about 4mm in aluminium and can be stopped by a one-quarter inch thick
sheet of aluminum. This indicates that the rays cannot be penetrated through the human skin.
However, there is great danger when the beta emission source gets inside someone. They can
cause fluorescence in some materials such as anthracene but not zinc sulphide. The emission of a
β– particle results in the formation of a new element that has its atomic number increased by 1
and its mass number remaining the same. An example is the emission of a β - particle from
thorium.
234 Th 234 0
90 91Pa + -1e

Gamma (γ) – rays

Gamma rays are not particles but a high energy form of electromagnetic radiation (similar to x-
rays or visible light but except more powerful). Gamma rays are energy that has no mass or
charge. Gamma rays have tremendous penetration power and require several inches of dense
material (like lead) to shield them. Gamma rays may pass all the way through a human body
without striking anything. They are capable of penetrating through layers of matter opaque to
ordinary light. They are considered to have the least ionizing power and the highest penetration
power. Their penetrating power allows them to penetrate about 100m through air and also 0.5m
of iron or lead. They can cause fluorescence in some materials such as sodium iodide and zinc
sulphide. Figure 11.1 shows the properties of these rays.

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 FIGURE 11.1 THE PROPERTIES OF THE MAJOR RADIOACTIVE RAYS
Alpha (α)– rays Beta (β)–rays Gamma (γ)– rays
Nature Helium nuclei, 42He Electron, 0-1e Electromagnetic radiation
Electrical charge +2 -1 No charge (0)
Mass 4unit ⁄ unit No mass (0)
Velocity About ⁄ the speed of Varies (from 3 - 99% of Speed of light
light speed of light )
Relative penetration 1 100 10,000
Absorber Thin paper Thin metal Large lead block

FIGURE 11.2 The effect of electric field on the three types of radiation

FIGURE 11.3 The three types of radiation and their absorbers

NATURAL RADIOACTIVE DECAY SERIES

Usually, elements (nucleus) formed during radioactive decay are also unstable and so would
disintegrate further until a stable element is formed. There are a series of changes that would
occur at varying rates, ranging from less than a second to millions of years before the final
formation of a stable element. There are three natural occurring radioactive decay series which
are named after the longest lived element in the series. They are;

The thorium series

The thorium series begins with thorium (23290Th) which has a half-life of 1.39 x 1010 years and
ends with the stable nuclide of lead (20482Pb) after 12steps of disintegrations through the emission
of alpha and beta particles. This series is sometimes termed 4n series because the mass number
of each of the series is exactly divisible by 4.

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FIGURE 11.4 The thorium series

The uranium series

The uranium series begins with uranium (23890U) which has a half-life of 4.5 x 109 years and ends
with the stable nuclide of lead (20682Pb) after 15steps of disintegrations through the same process
as in Thorium. This series can also be called 4n + 2.

The actinium series

The actinium series is named after its first-discovered member, actinium -227. The series
actually begins with uranium (23590U) and after about 13steps of disintegrations through the
emission of alpha and beta particles ends with lead (20782Pb). This series is also called 4n + 3
series.

The neptunium series

RATE OF RADIOACTIVE DECAY/ half - life

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Radioactive decay occurs at varying rates, ranging from less than a second to millions of years.
For a particular radioactive element, spontaneous disintegration usually occurs at the same rate
irrespective of the state or condition of the sample. That is a particular radioactive element would
emit the same type of radiation at the same rate regardless of its chemical state, applied pressure,
electromagnetic or gravitational field. Therefore, the rate of a radioactive decay can be used to
characterize a radioactive element. This rate follows a first order rate law that requires the rate of
radioactive radiation is proportional to the number of the radioactive atoms present. Given the
equation for a radioactive decay process;

A B+x +∆E

This rate is usually expressed in terms of half-life of the radioactive element. The half – life of a
radioactive element is the time taken for it to disintegrate to half the mass of the original size. In
other words half – life is the time taken for half of the radioactive element to decay.

128