COURSE NAME: INORGANIC CHEMISTRY

HEAC: 1104

INTRODUCTION

This branch of chemistry is concerned with all other elements other than carbon containing
compounds.

While organic substances principally have a maximum co-ordination number of 4 (e.g. CH 4),
inorganic substances feature elements with co-ordination numbers frequently exceeding 4,
and having a variety of oxidation states.

In accounting for the existence and in describing the behaviour of inorganic materials, the
following aspects will be considered:

Atomic and molecular structure

Chemical bonding
Other principles that allow an understanding of the structures and properties of
inorganic substances of all types.

Note that the periodic trends among elements are a result of the regular pattern in electron
configurations (arrangements) of atoms.

This course will therefore examine the early development of the periodic table and will help
you gain an insight into the historical background for our modern view of atomic structure.

We will also explore how the results of the wave mechanical description provide the basis for
latter treatments of bonding and spectroscopy.

Here we briefly consider atomic spectra

Derivation of spectroscopic formulae
Periodic trends and periodic physical properties such as ionization energies,
electronegativity, electron affinities, covalent and ionic radii, polarizability

The detailed course outline

Atomic Structure

Definition of atomic structure and the views of early workers.

Classical experiments
Electronic structure of an atom
Bohr’s model of atom.
Mass spectrometer.
Radioactivity
The Periodic Table

General survey of the historical background to the periodic table of elements

including works of Dalton, Newlands, Mendleev and Mosley.
Division in the periodic table into groups and periods and correlation of the
periodic table with electronic configuration of elements.
Physical properties of the periodic table (ionisation potentials, electron affinities,
covalent and ionic radii, electronegativity).
General survey of the descriptive chemistry of alkaline earth metals, group IV A
elements, halogens and transition elements.

Chemical bonding

Types of bonding (ionic, metallic, covalent, ionic, dative)

Shapes of molecules
Polarity of molecules
Hydrogen bonding and its implications in biological molecules.

References:

1. Basic inorganic chemistry by F A Cotton and Wilkinson

2. Chemistry Matters (1988) by Shriver D, Atkins PW & Langford CH
3. Basic inorganic chemistry by J D Lee

And any other inorganic chemistry textbook

ATOMIC STRUCTURE

Historical development of the atomic theory

It was the Greek philosophers Democritus and Leucippus who first considered the idea that
matter is made up of particles in about 400BC. This was later supported by Boyle and
Newton. The idea was however not accepted because there was no experimental evidence for
it.

In 1808, a Manchester school teacher, John Dalton restated and extended the older concepts.
He gathered experimental evidence with which people were convinced. In his Atomic
Theory, Dalton said that “matter is made up of atoms” and atoms were regarded as
indivisible particles and devoid (without) of internal structures. This sort of belief was
summarised in John Dalton’s famous atomic theory. According to Dalton,

 All elements were made of tiny indivisible particles called atoms.

 Atoms could not be created, destroyed or sub-divided.
 Atoms of the same element had the same properties and the same mass while
those of different elements had different properties and different masses,
 When atoms combined to form molecules, they did so in simple whole
numbers.
 All molecules of one compound were identical and different from the
molecules of all other compounds.

An atom was therefore defined as the smallest part of an element which can take part in a
chemical reaction.

By using Dalton’s theory, we can clearly understand that;

When a reaction occurs in a closed vessel, all the atoms present before the reaction are still
present after the reaction. They just merely become rearranged. Since the masses of the atoms
are constant, the total masses of the substances before and after the reaction should be the
same.

However, more advanced knowledge in recent years has led to modifications of Dalton's
original theory.

By 19th century, because of experiments in physics, it was soon realised that atoms were
divisible and electrical in nature.

Today, we know that an atom is composed of electrons, protons and neutrons.

Classical experiments

These threw light on the existence of particles from which the atoms are composed and how
these particles are arranged inside the atom.

From the beginning of 20th century, scientists knew that atoms could be made to give off tiny
electrically charged particles which they called electrons.

They knew that these were negatively charged, and that the remainder of the atom was
positively charged.

The classical experiments

The discovery of the electron

The electron was discovered by William Crookes in 1879. He observed that when a glass
tube containing two electrodes (Cathode and anode) is partially evacuated, and sufficiently
high voltage is applied, the negative electrode emitted light called cathode rays.

Crookes also observed that when high voltage is applied across the electrodes, a series of
changes occurs in the tube as the pressure is lowered:

 The gas glows with characteristic colour of the gaseous element.

 The beam of rays was observed to be moving from the cathode in a straight line.
 At pressure 0.001mmHg, the glow in the tube disappears.

Explanation

 The neutral element particles in the tube are dissociated into positive and negative
particles.
 Positive particles move to negatively charged electrode and negative particles move to
positively charged electrode.
 These moving particles can collide together i.e. positive particles can collide with
neutral particles and etc.
 In the process of collision, some of the kinetic energy is imparted (transferred) to
neutral particles, causing it to break into positive and negative particles.
 When positive and negative particles collide (combine) they release energy in form of
light.
 These changes occur at relatively high pressure when particles are close to one
another and therefore high probability of collision.

When the pressure is completely low and therefore the number of particles colliding and
combining is relatively low, the distance between them is greater and therefore collision
between them is much less probable, the energy released is much less to cause the glow.

This means that:

 The particles will have a great deal of kinetic energy when they strike the cathode.
 This causes the cathode to emit particles called cathode rays.
 These cathode rays travel away from the cathode in straight lines because they are in the
influence of intense electric field.

Assignment - read about properties of cathode rays

Early experiments with cathode ray tubes showed that cathode rays have these properties:

1. They travel in straight lines. An object placed in the path of the rays forms a sharp
shadow on a fluorescent screen.
2. They cause fluorescence in several substances.
3. They will penetrate a thin sheet of metal, e.g. they penetrate thin aluminium foil
which even hydrogen molecules and helium atoms (the smallest molecules and atoms)
cannot penetrate.
4. They possess kinetic energy and therefore have mass. The rays rotate a small light
paddle wheel pivoted between the anode and cathode; reversing the voltage reverses
the rotation.
5. They are deflected by a magnetic field.
6. They are deflected by an electric field. They are deflected away from the negative
and towards the positive plates causing the electric field. This again shows that the
rays have a negative charge.
7. They produce X-rays when they strike matter.

Most scientists had differing views about the nature of cathode rays.

Experiments showed that they were deflected by electric or magnetic fields suggesting that
they were charged.

Others thought that they were a new form of radiation with some properties similar to those
of light (a new kind of wave phenomenon). While, others believed that cathode rays might be
composed of particles. In 1897, J.J Thomson observed many properties of the rays including
the fact that the nature of the rays was the same regardless of the cathode material. He
summarised his observations and concluded that the cathode rays were not waves but
particles with mass. His findings are generally accepted as the discovery of what later became
the electron. He constructed a cathode ray tube such as the following:
 With his tube, he could quantitatively measure the effects of electric and magnetic
fields on a thin stream of electrons passing through the positively charged electrode.
1.76 x 108
His measurements made it possible to calculate value of coulombs per
gram as the charge to mass ratio for the electron.
Once the charge to mass ratio of the electron was known, anybody who could
measure either the charge or the mass of the electron could easily calculate the other
quantity.

Discovery of the Nucleus

LORD RUTHERFORD

The experiment was designed to examine the interior body of atoms (1910). He was able to
see how the mass of the atom was distributed.

Rutherford bombarded thin foils of various metals (Au, Pt and Cu) with alpha particles as in
the diagram below:

Observations

 Most of the alpha particles passed directly through the foil without deflection.
 A small % was found to be slightly deflected through about one degree consistent
with Thomson’s model.
 A few of the alpha particles were scattered through large angles. Some were reflected
back in the direction from which they had come.

In 1911, Rutherford was able to account for the observations.

  Since particles are positively charged, the few deflections that occurred were because
of the protons of the atom are collected in a heavy, small positively charged central
nucleus which makes up just a tiny fraction of the atom. Therefore, he postulated that
most of the mass of an atom and all of its positive charge reside in a very but
extremely dense region which he called the nucleus.
 Since most of the particles passed through the gold foil undeflected, most of the atom
is empty space and the electrons rotate in this space around the nucleus in the in the
same way planets rotate around the sun. Therefore, most of the total volume of the
atom is empty space in which electrons move around the nucleus.

In the experiments most alpha particles pass through because they don’t encounter the minute
nucleus. They merely pass through the empty space of the atom.

He therefore concluded that an atom has a nucleus in which its positive charge and mass are
concentrated.

The analysis led Rutherford to propose a model in which an atom consists of a very small
positively charged nucleus, in which most of the mass of the atom is concentrated,
surrounded by negatively charged electrons, so that the atom is electrically neutral.

Subsequent experimental studies led to the discovery of the positive particles (protons) and
the neutral particles (neutrons).

NEUTRONS

Neutrons were first predicted by Rutherford to account for difference in atomic mass and
atomic number. Then, they were finally discovered by Sir James Chadwick in 1932, by
bombarding a thin sheet of beryllium atom with alpha particles.

Chadwick found out that particles which had properties quite different from those of protons
and electrons were given off.

They were not deflected at all by electric and magnetic fields and therefore possessed no
charge. The particles had almost the same mass as a proton or slightly greater.

Since they were neutral particles, he called them neutrons. Later experiments showed that all
atoms contain neutrons apart from that of hydrogen.

9 4 1 12
Be+ He → n+ C
4 2 0 6

From the above experiments, it can be deduced that all atoms contain three principal
fundamental particles namely: protons, electrons and neutrons.
 LECTURE 2

ISOTOPES AND MASS SPECTROMETRY

Some elements have the same atomic number but different masses. This is majorly because
of the difference in the number of neutrons thus being referred to as Isotopes. Isotopes of an
element have chemical similarity and therefore cannot be separated by chemical means. Since
the masses of isotopes of an element differ,
one must resort to physical properties related to the mass to separate them. Therefore,
isotopes can easily be separated using the mass spectrometer.

Mass spectrometry (mass spectroscopy) is a technique used to determine relative atomic

masses and the relative abundance of isotopes, and for chemical analysis and the study of ion
reactions using a mass spectrometer.

Mass spectrometry is now one of the most commonly used tool for qualitative and
quantitative work.

1. The technique is used to assess the composition of a sample (both organic and
inorganic).
2. It is also useful in determining structures of complex molecules (structure
elucidation).
3. It is also helpful in the determination of isotope incorporation, which is important in
research where stable isotopic markers e.g2H, 13C, 14C, 15N, 18O, 37Cl or 35Cl, are used
in determining the fate of a compound in the body.

Operation of a modern mass spectrometer

A mass spectrometer is usually used during mass spectroscopy. It is an instrument for

producing ions in a gas and analyzing them according to their charge/mass ratio.

It mainly consists of the vapourisation chamber, ionisation chamber, acceleration chamber,

deflection chamber, the detector, amplifier and recorder.
The whole apparatus is evacuated of air particles that may produce unnecessary ions.

1. Vapourisation chamber

The sample is heated by a tungsten filament to vapourise it. The vapourised sample is then
introduced in the ionisation chamber.

2. The sample is ionized and collimated. Usually the ions are produced in several ways:

 By using heated filaments.

 By application of strong electrostatic field.
 By reaction with an ionized reagent.
 By direct emission of ions from solid sample that is deposited on the heated
filament.
 By vaporization from a crucible and subsequent electron bombardment.

3. The acceleration chamber.

The positive ions produced from the ionisation chamber are accelerated by a strong electric
field of varying potentials such that only positive ions with the same velocity/kinetic energy
but with different mass-charge ratio will pass through to the magnetic field.

4. The deflection chamber.

The magnetic field then deflects the ions according to their mass-charge ratio. The strength of
the magnetic field is varied such that ions of the same mass-charge ratio are focused onto the
detector.
5. The detector, amplifier and recorder

The ions are changed into sizeable electric currents which are sent to the amplifier for fine
tuning and then to the recorder where they are recorded into peaks that show relative
intensities of ions of a particular mass falling at the detector at that instant.
A mass spectrum is thus obtained consisting of a series of peaks of variable intensity to which
mass/charge ratio (m/e) values can be assigned.

Interpreting a mass spectrum

The mass spectrum

A mass spectrum is a plot of percentage abundance or relative intensity against mass to

charge ratio of the ions separated in a mass spectrometer.
The mass to charge ratio is however numerically equal to the mass of the ion since most of
the ions formed in a mass spectrometer have a single charge.

The mass spectrum is usually has vertical lines and each vertical line represents an ion having
a specific mass-to-charge ratio ⁄ and the length of the line indicates the relative abundance of
the ion.

Relative abundance refers to the relative intensity of each isotope of an element represented
as a ratio or percentage.

The tallest line is assigned an abundance of 100 and is referred to as the base peak. The
intensities of the other ions are measured relative to this line.

Consider the mass spectrum for neon below;

According to this spectrum, there are three stable isotopes of neon. These include neon-
20 21 22
20( Ne), neon-21( Ne) and neon-22 ( Ne). The peaks at 20, 21 and 22 are due to the ions
20 + 21 + 22 +
Ne , Ne and Ne respectively. These ions are formed by bombardment of the
gaseous atoms by electrons as shown below;

20 20 +
Ne(g)+e Ne (g)

21 21 +
Ne(g)+e Ne (g)

22 22 +
Ne(g)+e Ne (g)

20 +
The height of each peak is related to the relative abundance of each isotope of neon. Ne
20
has the highest peak so Ne is the most abundant isotope.

21 + 21
Ne has the lowest peak so Ne is the least abundant isotope.
The relative atomic mass of neon can be obtained using the mass spectrum.

The percentage abundances (proportion of isotope) should be obtained first

 RADIOACTIVITY

The spontaneous emission of high energy radiation is called radioactivity. Rutherford

revealed that some minerals like uranium emit three types of radiation namely: alpha (ά), beta
(β) and gamma (ℽ). Each type differs in its response to an electric field, alpha bends towards
the negative plate, beta towards the positive plate and gamma is unaffected. Alpha and beta
rays considered to be high moving particles, in fact beta particles are equivalent to cathode
rays. The alpha particles are more massive than alpha particles and are positively charged.
Beta particles have charge of -1 whilst alpha particles have a charge of +2. He further
concluded that gamma rays are high energy radiation similar to X-rays; it does not consist of
particles and carries no charge.

Assignment: Read about the properties of these radiations and nuclear reaction
equations.

RADIOACTIVE DECAY

The rate at which a radioactive isotope decays cannot be speeded up or slowed down by any
physical or chemical means. The rate depends on the identity of the isotope and the amount
of isotope present. Radioactive isotopes do not decay at the same rate. Some decay very
rapidly in a few millionths of a second and others can even take billions of years to decay.

All radioactive decay processes follow first order kinetics.

The rate of radioactive decay at time is directly proportional to the number of radioactive
atoms present. The rate of decay therefore decreases and continues to decrease as more and
more atoms break up.

Therefore if represent number of atoms, then;

 Rate of decay ∝ N

Activity of a radioactive sample is the number of disintegrations per second of a radioactive

sample.

The decay constant is the proportionality between the number of radioactive atoms and the
rate at which the radioactive atoms decay.

Half life

The time taken for a number of radioactive atoms to decay to ⁄ atoms is called the
half-life. The half-life of Radium is about 1600 years. This means that 1g of Radium decays
to 0.5g in 1600 years. 0.5g decay to 0.25g in a further 1600 years, and so on. Half-life is the
time taken for the amount of a radioactive sample to decay to half its original value.

Trial Questions

1. Aradioactivesampleofcaesium-136decaysfrom480countsperminuteto60counts per
minute in 42 days. Calculate its half-life.
2. The half-life of strontium-90 is 29 years. Calculate its decay constant.
3. The disintegration constant of lead-199 is . Determine its half-life.
4. A sample of wood has an activity of . A freshly cut wooden tree has an

activity of . Calculate the age of the wood sample. The half-life of

carbon-14 is 5600 years.

 5. Aradioactiveisotopedecaysatsucharatethatafter68minutes,onlyonefourthofits

original amount remains. Calculate its half-life.

Graphical representation of radioactive decay

The decay of a radioactive substance can be represented graphically by plotting various kinds
of graphs depending on data experimental data provided.

Note that in each of these graphs can be substituted with Activity (A), amount, Number of
moles, mass or counts
Assignment: Discuss the applications of radioisotopes.
LECTURE 3

ATOMIC SPECTRUM OF HYDROGEN AND THE BOHR THEORY

A spectrum can be defined as a range of electromagnetic energies arranged in order of

increasing or decreasing wavelength or frequency of electromagnetic radiation emitted or
absorbed by an atom or molecule.

An electromagnetic spectrum is the entire range of wave length or frequency of

electromagnetic radiation extending from gamma rays to the longest radio waves and
including visible light.

Types of spectra

Emission spectrum

If atoms are heated to sufficiently high temperatures, they emit light of certain wave lengths.
The emission of energy occurs as a result of electrons moving from higher energy levels to
lower energy levels. The observed spectrum consists of a number of coloured lines on a black
background. The spectrum is called an atomic emission spectrum. The emission spectra of
atoms provide evidence that the electrons are distributed around the nucleus in various energy
levels.

Absorption spectrum

If atoms absorb light of a certain wave length, black lines appear in the spectrum where light
of some wave length has been absorbed. The absorbed energy by the atoms causes energy
changes from lower to higher energy levels. The observed spectrum is called an absorption
spectrum.

HYDROGEN SPECTRUM

When electricity is passed through a discharge tube containing hydrogen at low pressure, the
hydrogen molecules break up to form single hydrogen atoms. The hydrogen atoms emit
radiations in the and ultraviolet, visible and infrared part of the spectrum. When the radiations
are analysed by a spectrograph, a line spectrum is formed. Each line in the spectrum
represents a definite wavelength of a radiation.

The wave length is given by the Rydberg equation,

1
λ (
1 1
)
=¿RH 2 − 2 . Where; RH is
n1 n2

Rydberg constant, and n1 and n2 being simple whole numbers and λ is the wavelength.

An explanation of the hydrogen spectrum

When the hydrogen atom absorbs energy, it causes the electron to experience a transition
from a lower to a higher energy level. The observed lines in the spectrum are due to
electronic transitions from the higher energy levels to the lower energy levels in the atom
with emission of energy. When an electron from jumps from a higher energy level to a lower
energy level, it emits energy equal to the difference between the energy of the two energy
levels in the form of small packets of light known as photons. For every transition of the
electron, there is a line in the spectrum and there are different types of spectral series formed.

Niels Bohr (1885-1962) attempted to account for the spectrum of hydrogen and hydrogen-
like species by proposing what is now called ‘the Bohr’s Model of the atom’

His model could account for hydrogen-like species such as He+, Li2+, etc.

He did this by accepting past postulates, rejecting others and by assuming new ones.

 Rutherford’s nuclear model that the hydrogen atom contains a nucleus, proton,
electron and a radius r.
 Theories of Planck and Einstein that E = hʋ were accepted.
 The electrodynamic theory (that a moving electron emits energy) was rejected.
  The electron was assumed to travel in circular orbits.
 Angular momentum of the electron was quantized.
 He proposed that energy is emitted or absorbed when an electron moves from one
orbit to another.

Prior to 1913, several experiments had been done to measure the frequency of various types
of light that could be absorbed or emitted by atoms.

It was already known that atoms characteristically absorbed or emitted light at defined
frequencies. Efforts to explain these observations centred mainly on the hydrogen atom
which was the simplest and had the simplest spectra.

In 1885, Balmer showed that the wavelength  of any line in the visible region of the
spectrum of atomic hydrogen could be given by a simple empirical expression:

1
λ (
1 1
=R H 2 − 2
2 n )
Where RH is Rydberg’s constant and n has values 3, 4, 5 etc. The lines observed in the visible
region are called the Balmer series but several other lines may be observed in different
regions of the spectrum i.e

Series Region of the spectrum

Layman UV
Balmer Visible/UV
Paschen IR
Brackett IR
Pfund IR

Similar equations were found to hold for the lines in the other series in the hydrogen
spectrum. i.e

1
λ
1 1
( )
Layman, ν= =R H 2 − 2 n=2, 3 , 4 ,5 .. .
1 n

1
λ
1 1
( )
Balmer , ν= =R H 2 − 2 n=3 , 4 , 5, 6. ..
2 n
 1
λ
1 1
( )
Paschen, ν= = RH 2 − 2 n=4 ,5 ,6 , 7. ..
3 n

1
λ
1 1
( )
Brackett , ν= = R H 2 − 2 n=5 ,6 , 7, 8 .. .
4 n

1
λ
1 1
( )
Layman, ν= =R H 2 − 2 n=6 ,7 , 8 , 9.. .
5 n

Earlier on, attempts had been made to obtain a physical picture of the atom.

JJ Thomson as we saw had shown that application of high electrical potential across a gas
gave electrons, suggesting that these were present in atoms.

Rutherford had also suggested that an atom consisted of a heavy positively charged nucleus
with a sufficient number of electrons around it to make the atom electrically neutral.

The Bohr’s model of the hydrogen atom

Since Rutherford‟s model of an atom could not explain that facts as to why the atomic
spectra consisted of separate lines. The model did not explain why atoms absorb or emit light
of certain frequencies. In his model too, Rutherford could not explain why the spectral lines
converge to form a continuum.

Niels Bohr combined all the above ideas and suggested that the atomic nucleus was
surrounded by electrons moving in orbits just like planets around the sun.

In an effort to explain the spectrum of atomic hydrogen and hydrogen-like species (H, He +,
Li2+, Be3+, Na10+, Mg11+ etc), Niels Bohr proposed what is now called the "Bohr Model" of the
atom.

This model was a very important stepping stone in the development of modern description of
atoms.

In 1913, Niels Bohr put forward his theory that explained these facts. He based on Planck‟s
quantum theory which fundamentally proposed that matter cannot absorb or emit energy in
continuous amounts, but only in small discrete units called quanta. To be able to explain
atomic line spectra, Niels Bohr developed an atomic model based upon the quantum theory.
He made some postulates described below:
The Bohr atomic model

Postulate 1

The hydrogen atom consists of a nucleus containing a proton (and therefore having a charge
of +1), and an electron (with a charge of -1) moving round the nucleus in a circular orbit of
radius r.

Postulate 2

He proposed that electrons do not radiate energy as they orbit around the nucleus, but exist in
states of constant energy that he called stationary states.

Postulate 3

Bohr explained that as long as the electron stays in that orbit, it neither absorbs nor radiates
energy. He further explained that electrons can be moved into different orbits with the
addition of energy. On returning to their ground state they emitthe corresponding amount of
energy- aquantum of light or photon.
In summary, the Bohr Theory accounts for the hydrogen spectrum in the following manner.

 When hydrogen atoms are excited, their electrons occupy orbits having higher
energies.
 When an electron returns to a more stable orbit, it emits photon of energy
corresponding to the energy difference between the orbits.
 The transition back to the ground state can occur directly or stepwise, one photon or
several.
 When an electron is excited to an orbit with higher energy level (n > 1) and then drops
back to an orbit with n = 1, then UV series is obtained i.e. Lyman series.
 When an electron is excited to orbits with higher energies and drops back to an orbit
with n = 2, visible series is obtained, i.e. Balmer series.
 When the electron is excited to upper orbits with higher energies and drops back to
orbits with n = 3, infrared series is obtained i.e. Paschen series.

All the above information is summarised in the figure below:

Problem

The line of greatest wavelength of a particular series in the atomic spectrum is at 6563A o.
What is this series? [RH = 109,678 cm-1]

Solution

The question asked requires knowledge of whether the series belongs to Lyman, Balmer or
Paschen series. We must sort out the line of greatest wavelength first.
The lines of greatest wavelengths are :

Lyman n = 2 to n = 1

Balmer, n = 3 to n = 2

Paschen, n = 4 to n = 3

By substituting for Lyman in the equation

1
λ [ ]
1 1
=R H 2 − 2
nf n i

1
−8
6563 x 10 cm
1 1
=109 ,678 2 − 2
1 2 [ ]
15230≠82, 259

This cannot be Lyman series since the right-hand side of the equation is not equal to the left-
hand side.

Substituting for Balmer series,

1
−8
6563 x 10 cm
=109 ,678
1 1
2
2 3
− 2
[ ]
 15230≈152,233

Agreement in the case of Balmer substitution, suggests it is Balmer series.

Assignment

Calculate the wavelength of the first line and the series limit for Lyman series for hydrogen
(R = 109, 67800m-1)

1
λ
=109 , 67800
[ 1 1
]
2 − 2 =8225900 m
1 2
−1

λ=1 .2157 x 10−7 M

1
λ
=109 , 67800
[ ]
1 1
1
2 − ∞ =10967800 m
−1

The series limit is then

λ=9. 117 x 10−8 m

Bohr’s model achieved considerable success in interpreting experimental results. His model
however, had shortcomings too.

1. It could not deal with atoms more complicated than hydrogen-like ions.
2. It regarded an electron as discrete with defined positions and velocity. The
electron is therefore considered as a particle. As a consequence of these two
shortcomings, his model was almost abandoned.

Heisenberg’s Uncertainty principle

According to De Broglie, moving electrons had waves of definite wavelength associated with
them. Further experiments showed that a stream of electrons could be diffracted just as X-
rays can. Since it is only possible to account for diffraction in terms of waves, it was
necessary to assume that a stream of electrons behaves as a wave-like radiation.
As far as atomic structure is concerned, the idea of tiny, negatively charged particles existing
in fixed orbits around the nucleus of an atom is replaced by the idea of charge clouds of
varying charge density existing in a wave like pattern around the nucleus.
An electron can no longer be considered to occupy a specific, limited orbit but instead it
exists in a much more diffuse region known as atomic orbital.

An electron is different from a larger particle in a way that its wave-like nature is of much
greater significance than the wave-like nature of the larger particle.
The other difference is that both the position and the velocity of a large particle like a planet
can be measured with reasonable accuracy. However, there is no way of measuring the
velocity of an electron exactly and locating it exactly at any one time. This is because any
method used affects the electron being measured.

The information which can be obtained about an individual electron is therefore far from
precise. Thus Heisenberg Uncertainty Principle in 1927 which states that;

The more accurately the position of a particle is defined, the less accurately is its velocity
known, and the more accurately the velocity is defined, the less accurately is its position
known.

Therefore, in order to define an electron with respect to its energy and position in an atom
and to explain the complex spectra of elements, we need four quantities known as quantum
numbers.

Quantum numbers

The term quantum number is used to label the various energy levels. A set of four quantum
numbers are used to describe completely the movement and trajectories of each electron
within an atom. Each electron in an atom has a unique set of quantum numbers and no two
electrons can share the same combination of the four quantum numbers. Quantum numbers
are important in determining the electronic configuration of an atom and the location of the
electrons in the atom. They are also used to understand other characteristics of atoms such as
ionisation energy and atomic radius.

Quantum numbers are a set of four integers which are necessary to locate the energy level or
position of an electron and to specify the size, shape and orientation of orbital.

In atoms, there are a total of four quantum numbers. These include;

1. Principal quantum Number (n): The electron can only be in some well-defined
stationary Bohr orbits where its average energy would also be fixed.

These orbits are numbered 1,2,3,4 ... starting from that nearest to the nucleus and are
indicated by letter n.
These are also labelled, by letters K, L,.M,. N. corresponding to quantum number (n) to
indicate in which level or orbit the electron exists.

The value of n represents the size of an orbit. This quantum number decides the energy of the
electron in the orbit and has only positive integral values except zero.

The principal quantum number enables us to ascertain the maximum number of electrons (N)
which could be accommodated in that, level of orbit or shell by the relation N = 2n2

Thus

Principal quantum number Level of shell Maximum number of

electrons accommodated
therein, N=2n2
1 K 2
2 L 8
3 M 18
4 N 32
5 O 50

(2) Azimuthal quantum number (l): A Stationary Bohr orbit is really made up of
number of sub-levels. For the given principal quantum number n, the number of available l
values is also n dependent. Thus, for a given number n, the allowed values of l are 0,1,2,3 ...
(n-1). These allowed sub-levels are denoted by letter s, p, d, f ... corresponding to l =
0,1,2,3,.. respectively. i.e

Principal quantum Values of l[l = 0, 1, 2…(n-1) Corresponding sub-levels

1 (K Level) 0 s
2 (L Level) 0, 1 s, p
3 (M Level) 0, 1, 2 s, p, d
4 (N Level) 0, 1, 2, 3 s, p, d, f

The electron having l = 0 is an s-electron. When l = 1, it is a p-electron; when l = 2 it is d-

electron and so on.

3. Magnetic Quantum Number (m): It was shown by Zeeman that the spectral lines
are split up into more lines by application of magnetic field. To explain this splitting of
spectral lines, a new quantum number was introduced, known as magnetic quantum number
m. This can have as many as (2l + 1) different values for a given value of l starting from -l to
+l through zero. Thus, if l= 3, m = -3, -2, -1.0, + 1, +2, +3 i.e a total of 7 values are possible.

4. Spin Quantum Number (s): While moving in its orbit, the electron also rotates about
its own axis. This spin may be clockwise or anti-clockwise. Electron having the same three
quantum numbers (n, 1 and m may have a clockwise or anti clockwise spin.
Thus,

N Allowed values of l Total allowed values of Possible values of m

m = (2l + 1)
I(K) 0 (s) 1 0
0
2 (L) 0 (s) 1 0
1 (p) 3 -1, 0,+1
3 (M) 0 (s) 1 0
1 (p) 3 -1, 0,+1
2 (d) 5 -2, -1, 0,+1,+2
4 (N) 0 (s) 1 0
1 (p) 2 -1, 0. +1
2 (d) 5 -2, -1.0, +1.+2
3 (f) 7 -3, -2, -1, 0.+1
+2, +3

The electron is given an additional quantum number called spin quantum number denoted

by s. Two values + and - are assigned to s.

It is thus seen that an electron can be fully described for its position and energy by four
quantum numbers, n, l,m. and s.

In summary,

(i) The principal quantum number n indicates the main energy level to which the
electrons belong.

(ii) The subsidiary (sub-level) quantum number 1 indicates the sub-level to which the
electron belongs. Each value of this is associated with a 'probability distribution' of a
particular shape.

(iii) The magnetic quantum number is related to the orientation of 'probability

distributions' of electrons with a given sub-level number l.

(iv) The spin quantum number s indicates the direction of electron spin.

Consider the hydrogen atom in its ground state. Then the orbital electron is in the first main
energy level, that is n = 1

Now l can have values n- 1, 0. Therefore in this case l = 0

 Again, m can have values l….. 0…….-l. Therefore in this case m = 0

1 1 1
s can be either + 2 or - 2 . Since there is only one electron let s = + 2
The quantum number
1
The electron is now labelled by the four quantum numbers n = 1, l = 0, m = 0, s = + 2
.

Distribution of Electrons

Pauli's Exclusion Principle

The four numbers n, l, m and s are required to designate an electron. This rule imposes a
restriction on the values of four quantum numbers of various electrons in the, same atom and
states that "no two electrons in the same atom can have the same values of all the four
quantum number", i.e. they must differ at least in the value of any one of them.

Pauli's Exclusion Principle enables us to find the number of electrons which could be
accommodated in the various shells and sub-shells.

The maximum number of electrons in different quantum levels are 2 for K-level, 8 for L-
Level, 18 for M-level and 32 for N-level.

Electron configuration of elements

Distribution of electrons in shells and sub-shells for complicated atoms is governed by certain
rules. As discussed earlier, each electron shell can have a maximum number of electrons
given by 2n2. As each electron shell has sub-shellsand their energy difference is very much
less, the sub-shellshaving lower energy are filled first. It is seen that the order of energy of
various sub-shells is the following

1s < 2s < 2p <3s < 3p < 4s <3d <4p < 4d < 5p < 6s < 4f <5d < 6P < 7s < 5f "< 6d

The above order can be represented in a simple way: (Aufbau principle – give it). This is the
building-up principle
In filling electrons in the atom, a fundamental rule, Pauli’s exclusion principle must be put
into account i.e. "No two electrons in one atom can have an identical set of quantum
numbers."

What it means is that no electrons should have the same "address". In short, any one orbital
can take up electrons only, on condition that these electrons have opposite spins.

This introduces us to Hund’s rule of maximum multiplicity:

It states that when electrons are present in a number of degenerate orbitals, they occupy all
the orbitals singly with parallel spins before any pairing in any one orbital occurs

Questions

Write the electronic configuration of the following;

1) Potassium

2) Sodium

3) Chromium

4) Iron (III) ion

5) Copper (I) ion

Lecture 4

THE PERIODIC TABLE

The historical development of the Periodic Table

Prout, an Englishman, made the earliest attempt to show a connection between atoms of
different elements. This was in 1815, seven years after the publication of the atomic theory.
He found out that the many atomic weights determined by Dalton, Berzelius and others were
approximately whole number multiples of the atomic weight of hydrogen. Prout therefore
suggested that atoms of different elements were composed of hydrogen atoms in various
numbers. This whole number rule as however abandoned soon.

In 1858, Cannizzaro introduced a method of finding relative atomic masses. Chemists soon
observed a periodic relationship between the properties of elements and their relative atomic
masses.
In 1864, Newlands showed that if elements were arranged in order of their atomic weights,
elements with similar properties appeared in intervals. Part of his table is shown below.

Elements that were chemically similar such as lithium, sodium and potassium usually
occurred in every eighth position. From his observation, Newland put forward the following
periodic law; the properties of elements are a periodic function of their atomic weights.

Newlands‟ law however did not convince majority of the chemists. This is because some
elements were placed in the table but assigned incorrect relative atomic masses. In addition,
no allowance was given for the possibility of the undiscovered elements.
In 1869, the Russian chemist, Demitri Mendeleeff, used Newlands basic idea to devise a new
kind of table. He arranged all the known elements in order of their relative atomic masses to
show the relationships between the elements more clearly. He improved Newlands‟ table by;

1. Leaving gaps in the Periodic Table on a prediction the new elements would be

discovered to fill the gaps. He predicted the properties of the undiscovered elements.
When the elements were discovered and found to have relative atomic mass and the
physical and chemical properties Mendeleeff predicted, chemists strongly believed in
his Periodic Table.

2. Introducing long rows periods for the elements now called transition elements. This
implied that the elements were not placed under nonmetals as in Newlands‟ system.
Below is part of Mendeleef‟s Periodic Table;
More elements were soon discovered including the noble gases which now make the Modern
Periodic Table.

Unique position of Hydrogen in the Periodic Table

The position of hydrogen in the Periodic Table is a great source of argument. Whereas some
authors place it above lithium in group I, others place it above fluorine in group VII. Others
place isolate it to a central position to indicate that it is unique and has no genuine analogues.

From its electronic structure, , hydrogen resembles group I elements which have one electron
in the outermost sub energy level. Hydrogen is also similar to group I elements in being
electropositive because it is liberated at the cathode when aqueous solutions of acids are
electrolyzed.

Also just like group VII elements, the hydrogen atom is one electron short of a noble gas
configuration. Therefore hydrogen resembles elements in both groups in being consistently
monovalent when combining with other elements.

The properties of hydrogen relate it much more to the halogens than alkali metals. It has a
much higher ionisation energy and electronegativity than alkali metal. This gives it a
nonmetallic character. It also resembles halogens by existing as diatomic molecules. Just like
salts of halogens, when fused metallic hydrides liberate hydrogen at the anode on electrolysis.

The Modern Periodic Table

The structure of the Modern Periodic Table

In the modern Periodic Table, elements are arranged in order of increasing atomic numbers
instead of atomic mass. Atomic numbers increase from left to right and from top to bottom in
the table. The modern Periodic Table has more elements than Mendeleef‟s table because
many elements have been discovered since his time. The elements can be classified in three
classes; metals, metalloids and non-metals.

In the modern Periodic Table, each element is represented by its chemical symbol, atomic
mass and mass number. The rows in the table are called Periods and the columns are the
groups. The table has a total of 18 groups and 7 periods.
The first period has only 2 elements. The second and third periods have 8 elements each. The
fourth and fifth have 18 elements each. The sixth has 32 elements. The seventh period has 32
elements including Nihonium-113, Moscovium-115, Tennesine-117 and Oganeson-118.
These new elements were approved in 2015 by IUPAC and added to the table to complete the
seventh period to 32 elements.

There is a separate group of elements at the bottom of the table. It consists of 14 elements of
the sixth period called the lanthanides and 14 elements of the seventh period called the
actinides.
Elements in the same group have similar chemical properties and the same outermost
configuration.