UNIT1 (WEEK 1-5)

1.1 ATOMIC THEORY AND NATURE OF ATOMS

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.
An atom is the smallest particle of an element that can take part in chemical
reaction. A molecule is the smallest particle of a compound which can exist on its
own. A molecule can be made up of two or more atoms of the same or different
elements.

1.2 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 matter is made up of tiny indivisible and indestructible particles called atoms
2. Atoms can neither be created nor destroyed.
3. Atoms of the same elements are exactly alike (identical) in size, shape, mass and
chemistry and differs from atoms of other elements.
4. Atoms of different elements combine to form a compound, the number of atoms
combined bears simple ratio.

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.
1.2.1 Modern Atomic Theory
i. All matter is composed of subatomic particles such as electrons, protons and neutrons
(meaning that atoms are divisible) ii. In nuclear reactions, atoms are created, divided or
destroyed. In ordinary chemical reactions, there may be small changes in mass due to energy
changes.
iii. All atoms of the same element may not have same mass (due to isotopes). iv.
Giant molecules exist which contain thousands of atoms.

1.3 EXPERIMENTAL EVIDENCE OF ATOMIC STRUCTURE

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. The tube began to glow, when the voltage is increase, a green colour
glow appeared on the tube. It was proved by Thompson that the glow was as a
result of rays that move in straight line from the cathode, thus the rays are called
cathode rays.

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 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.
FIGURE 1.1 THE CATHODE RAY TUBE

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 and cast shadows of
opaque objects
placed in their paths.

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 X10 11
C/kg. 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 =
 = 9.10 × 10-31 kg
Discovery of protons
Atoms are electrically neutral. If atoms contain negatively charged electrons, then
they must also contain enough positively-charged particles to make the atoms
neutral. These positively charged particles are called proton.
Thompson repeated his experiments, but used a discharge tube with central cathode
which had a hole in it. He noticed a reddish glow in the opposite direction to the
green glow (cathode rays) and proved that the green glow was due to positively
charged rays. Thompson determined the charge- to – mass ratio of proton to be
9.58 × 107 C/kg which 1840 times greater than that of electrons.
Thompson’s Model of Atom
When J.J. Thompson (1897) discovered electrons, it became evident that atom was
not the smallest unit of matter. In 1904, Thompson suggested a model of atom as
sphere of positive matter in which electrons are positons by electrostatic force. He
called this model the “plum pudding model” or “watermellon” and is shown in
figure 1.2.

FIGURE 1.2 THE PLUM – PUDDING MODEL

1.4 RUTHERFORD EXPERIMENT

Discovery of the nucleus
Lord Rutherford and two research assistant, Gieger and Marsden between 1912 and
1913 conducted an experiment to find out more about the structure of atoms. The
scientist fired fast-moving alpha particles, which are positively charged helium
(He2+) particles, at very thin sheet of gold foil.
 FIGURE 1.3 A MODEL OF RUTHERFORD GOLD-FOIL EXPERIMENT
Most of the alpha particles passed straight through the foil without suffering any
deflection, while some were scattered through very large angles. A few particles
bounced right back.

FIGURE 1.4 THOMPSON VS RUTHERFORD

To account for the observation in the gold foil experiment, Rutherford proposed a
nuclear theory of atom. According to this theory, atom consists of positive core
called the nucleus, where mass of atom is contained, and electrons, which move
around the nucleus. The model of atomic structure as put forward by Rutherford
has been compared to solar system. Rutherford concluded that:
i. atom consist of largely of empty space; ii. all the protons were
the nucleus of the atom; iii. electrons orbited around the nucleus like
planets around the sun.

Limitations of Rutherford Model

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.

1.5.4 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.
𝟗
𝟒𝑩𝒆
𝟒
+ 𝑯𝒆 (α) →
𝟐
𝟏𝟐
𝑪+
𝟔
𝟏
𝟎𝒏
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 understand. However, because of some shortcomings of the Bohr
model, the quantum mechanical model is more valid.
1.5.1 THE 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 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;
𝒄
ƒ = ƒλ = c
𝛌

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 10 8 m/s.) λ
= wavelength

In 1900, Max Planck has postulated that energy that ejected electrons from a
metallic atom was radiated in units or packages, each called a “quantum of
energy” and that this energy was not radiated continuously as had been previously
thought. Albert Einstein 1905 called this quantum of light energy a photon. The
energy carried by a photon is related to its frequency by the expression;
E = hƒ but ƒ =
𝒄
𝛌

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

107meters.

Solution: using the relation ƒ = 𝑐

λ
8
c =3 x 10 m/s λ=
6.5 X 10-7m

ƒ= = 4.6 x 1014 hertz

Example 1.2 Calculate the frequency and energy of a photon having a wave length
of 1. 7μm.

Solution: ƒ = 𝒄
𝛌

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

ƒ= = 1.77 × 1014hertz
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

De-broglie in 1924 was the first person to observed that light and matter exhibit a
wave- particle duality, i.e light and matter have a wave –like and particle- like
properties.
As a wave, using Max Plank’s equation, E = 𝒉𝒄 …………………(i)
𝛌

As a particle, using Albert Einstein equation, E = mc2 ……………(ii)

 But ∆mc = ∆p
Where m = mass

where h = 6.626 × 10-34 J

∆p = change in momentum
c = speed of light λ = de-
broglie wavelength
Example 3. Calculate the De-broglie wavelength for an electron travelling at the
speed of
i. Speed of light
ii. One- third the speed of light (take the speed of light to be 3.0 × 108 m/s)
Solution c = 3.0 × 108 m/s h = 6.626 × 10-34 J
Me = mass of electron = 9.1 × 10-31 Kg

(i)

= 2.427 × 10-12m (ii)

c= m/s = 1 × 108 m/s

1.5.3 THE HYDROGEN SPECTRUM

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. These series of lines are named after
their discoverers. They are as shown in table 1.3 below;
TABLE 1.3 THE FIVE SERIES OF LINES IN THE SPECTRUM OF HYDROGEN
ATOM

O Seri Cove n n2
de es rage
r towa
rd
Fir Lym Ultra 1 2,3
st an viole ,4,
se serie t 5,--
rie s regio ---
s n ∞
Se Bal Visib 2 3,4
co mer le ,5,
nd serie regio 6,--
se s n ---
rie ∞
s
Th Pasc Infra 3 4,5
ird hen red ,6,
se serie regio 7,--
rie s n ---
s ∞
Fo Brac Infra 4 5,6
urt kette red ,7,
h . regio 8,--
se n ---
rie ∞
s
Fif Pfun Infra 5 6,7
th d red ,8,
se serie regio 9,--
rie s n ---
s ∞

Figure 1.6 showing the energy level in hydrogen atom and the electronic transitions that
give to the spectrum
The wave length (λ) of the radiation is related to the frequency (ƒ) by the equation

𝑪
λ=
ƒ

ƒ (or v) = frequency of radiation express as hertz (Hz) is equivalent to cycle “per

second”
c = speed of light (3 x 10 8 m/s.) λ
= wavelength (m)

In spectroscopy, frequency is expressed as wave number ( ∇) and the wave number

is the reciprocal of wave length.

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:

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

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(

) = 8225907m-1
m

Second line )=R(

) = 10967876X 0.89
1

= 1.024 X 10-7m
Third line ) = R (

= 9.73X 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 108m/s Solution:
Frequency ( )=R(
For the Balmer series, n1= 2 therefore, the second line has n 2= 4 and the third line
has n2= 5. Substituting these values into the Rydberg equation we have;
Second line ) = R (

) = 10967876X (
 ) = 10967876X (

= 4.863X 10-7m
Energy of transition E =
λ

E=(
Third line ) = R (

) = 10967876X (
) = 10967876X (
) = 10967876X 0.21
1

= 4.34 X 10-7m
Energy of transition E =
λ

E=( j

QUANTIZATION OF ELECTRON IN A HYDROGEN ATOM

In 1926, Erwin Schrondiger brought about an equation called Schrodinger

equation, the central equation of quantum theory. This equation takes into account
the wave nature of particles as proposed by de-Broglie 1924. The equation also
suggested that electron can be taking from one energy level to another.

By assigning various values to n, we can evaluate the corresponding energy of

electron in the orbits of hydrogen atom using equation

E= - ……….i

When this is done, we find the energies of several orbits as follows:

n=1, E = - 2.18 × 10-18J
n=2, E = - 0.545 × 10-18J n=3,
E = - 0.242 × 10-18J n=4, E=
- 0.13625 × 10 J n=5,
-18
E=-
0.0872 × 10-18J n=6 E=-
0.0606 × 10-18J
n= ∞, E= 0

Equation……i can be written as

En ……..ii
Where En is the energy value of n in the hydrogen spectrum

E J

Example 1.5: use Bohr’s theory to calculate the wave number of the first lines in
the Paschen and Bracket series in the hydrogen spectrum.

Solution
For the first line series in the Paschen series, n1 =3, n2 = 4

Using Bohr’s theory equation; En When

n

E J
When n2 = 4, we have ;

E J
∆𝑬 = E4 - E3
∆𝑬 = - 0.13625 × 10-18 - 0.242 × 10-18 = 0.10575 × 10−18𝐽
1. 8797 × 10-6 m
Wave number = 5.32 × 105 m-1
For the first line in the Braket series, n1 =4, n2 = 5
Using Bohr’s theory equation; En When
n

E J
When n
E J

∆𝑬 = E4 - E3
∆𝑬 = - 0.0872 × 10-18J- 0.13625 × 10-18 = 0.04905 × 10−18𝐽
6m

Wave number = 2.47 × 105 m-1

1.5.4 HEISENBERG’S UNCERTAINTY PRINCIPLE

To further understand the atomic structure, the electron was treated as wave not as
a particle. It was established that it is difficult to determine with certainty the
position and momentum of an electron. Hence 1927, Werner Heisenberg came up
with a relationship between the position and momentum of an electron.

Heisenberg’s uncertainty principle states that, it is difficult to describe precisely the

position and momentum of small bodies like electrons.

The uncertainty of position of small body like electron (∆𝑥) and the uncertainty of
describing the momentum of electron (∆𝑝) or (∆𝑚𝑣) is given by the Heisenberg
equation;

Where h= plank’s constant

But ∆𝑝 = ∆𝑚𝑣
hence, ∆

also, ∆ where ∆𝑣 = uncertainty velocity, m= mass of the electron

Example 1.5. Calculate the uncertainty in position, if the uncertainty in velocity is
 2.5 × 103 ms-1 (h = 6.63 × 10-34 kgm2s-1 and m 9.1 × 10-31kg)

Answer = ∆𝑣 × ∆𝑥 ≥ 2.3 × 10-8 m

1.5.5 BOHR’S POSTULATE

The summaries of Bohr’s postulates areas follow:-

1. The electron moves in circular orbits at different energies around the nucleus.
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 E f, 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.

1.5.6 SUB-ATOMIC PARTICLES

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.

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 1.1: THE PRPERTIES OF SUBATOMIC PARTICLES

Pa Sy M Rel Re
rti m as ativ lat
cle bo s e ive
l (g elec At
) tric o
al mi
cha c
rge m
ass
(a.
m.
u)
El e- 9. -1 1
ect 09
ro 1 1840
n x1
028

Pr P+ 1. +1 1
ot 67
on 25
2
x1
024

Ne n0 1. 0 1
utr 67
on 49
5
x1
024

Note: a.m.u is atomic mass unit

OTHER SUB-ATOMIC PARTICLES

Beside electron, proton, and neutron many other subatomic particles such as
Meson, Positron, Neutrinos and Anti proton have been discovered. A great deal
 of recent research is producing a long list of still other sub-atomic particle such as
quarks, pions and gluons making the picture of the atom more complex.

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. Complete the table below:

E Ato A C D
m
or
ion
of
ele
me
nt
1 Ma 1 3 -
ss 0 9
nu
mb
er
Nu 5 - 2
mb 0
er
of
prot
on
9

9
- Nu - 2 2
mb 0 0
er
of
neu
tron
7. What is the atomic mass of chlorine, if 3517𝐶𝑙 has a relative abundance of 75% and 3717𝐶𝑙
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
ii. Which line in the series is it?
 UNIT 2 (WEEK 6)
2.1 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.

2.2 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 2.1: Energy level of an atom

2.3 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:
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.

Figure 2.1 structure of atom with different energy levels

Azimuthal or subsidiary or angular momentum quantum number (𝑙ι): 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 sub-shells increases as the value of increases.
Azimuthal quantum number has integral values ranging from ι𝑙 = 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 2.1Summary of subshells, number of orbitals, shape of orbitals and their

maximum number of electrons
Subsh Numb Shapes Maximu
ell er of of m
orbital orbitals number
s of
electron
s
s 1 Spheric 2
al
 P S Magneti
p r u 3 c Dumbb 6
i b Quantu ell
d n s 5 m Double 10
c i number dumbbe
i d (m) ll
f p i 7 Comple 14
a a x
l r
q y
u Q
a u f
n a
t n l
u t
m u
N m t
u N
m u
b m Table
b s2.2:
Relationship between Quantum Numbers and Atomic orbital
Num
beroe

e
c
 P S Magneti
r u c
i b Quantu
n s m Table
c i number 2.2:
i d (m)
p i
a a
l r
q y
u Q
a u f
n a
t n l
u t
m u
N m t
u N
m u
b m
b s
Relationship between Quantum Numbers and Atomic orbital
Num
beroe

e
c
 ron2

8 e e
r r
(
l
)
1 0 0

2 0 0
1 -1,0,+1

3 0 0
1 -1,0,+1
2 -2,-
1,0,+1,+
2

4 0 0
1 -1,0,+1
2 -2,-
3 1,0,+1,+
2
-3,-
2,1,0,+1,+
2,+3

1
8

3
2
 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).
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.
Exercise: Can you write the number of orbitals in:
(i) The fourth energy level n = 4
(ii) (ii)The 4s orbital

2.4 Shape of Orbitals

An orbital is a region in space around the nucleus with high probability of finding an electron
with certain amount of energy. Each of the energy sub-level s, p, d and f has its own orbital
with characteristics.

a. The s-orbital: an s-sublevel has only one orbital: it is called s-orbital. It is spherically
symmetrical about nucleus. Its size and energy depend on principal quantum number, n. The
higher the n value, the larger the orbital size. The comparative sizes of s-orbitals are:
1s
< 2𝑠 < 3𝑠 < 4𝑠
 Figure 2.2 shape of s-orbital
b. The p-orbitals: A p-sublevel has three orbitals; they are collectively called p-orbitals.
Each of the p-orbital has a dumb-bell shape with the electron density concentrated on
both sides of the nucleus.

Px Py Pz
Figure 2.3 shapes of different p-orbital
c. The d-orbitals: There are five d orbitals, referred to as d z2, dxy, dxz, dyz , and dx2-y2. The d
orbitals are what give transition metals their special properties. In transition metal ions
the outermost d orbitals are incompletely filled with electrons so they can easily give and
take electrons.

2.5 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;

2.5.1 AUFBAU’S PRINCIPLE OR BUILDING -UP PRINCIPLE

The Aufbau’s principle is: Electrons go into orbital with the lowest energy before
occupying higher energy level. This means 1s orbital has to be filled before 2s
orbital is occupied. The order of filling the orbital is in accordance with the relative
energies.

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.

 2.5.2 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

The Pauli’s exclusion principle ( has 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.

2.5.3 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.
 UNIT 3 (WEEK 7)
IONIC CRYSTALS: STRUCTURE AND BONDING

Ionic crystal consists mainly of charged species usually made up of cations and
anions of different sizes. This result into inter particles forces being much stronger
than those in molecular and covalent crystals.

To maximize the attractions, cations are surrounded by as many anions as possible

and vice –versa, with the smaller of the two ions lying in the spaces (holes) formed
by packing of the layer. Ionic crystals adopt several crystal structures but many use
the Cubic closssest packing (CCP).

The methods for the determination of ionic crystal have been grouped into;
I. Diffraction method
II. Spectroscopy method

X-Ray Diffraction
This is phenomenon of interference and diffraction of light. There are many
examples of interference of light; among them are the varieties of colour seen in
films of oil and the effect on the rays of light when sunlight enters into narrow slit
in door or window.

Diffraction grating depends on the effects of transparent spaces between the rule
lines or distance apart on the wavelength of light to be diffracted. Since crystal is
composed of particles (atoms, ions or molecules) which are generally arranged in a
regular pattern, the possibility arises that it may behave as a 3-dimensinal
diffraction grating of radiation of suitable wavelength.
X-Ray Diffraction by Crystals

X- ray diffraction is the scattering of X-rays by the unit of a crystal lattice. The
scattering or diffraction patterns produced are used to deduce the arrangement of
particles in the solid lattice.

An arrangement for obtaining the x-ray diffraction pattern of a crystal will be;

Shield must be present in the above setup to prevent strong undiffracted x—rays
from damaging the photographic plate.
A beam of x-ray is directed at a mounted crystal. Atoms in the crystal absorb some
of the incoming radiation and then re-emit it, the process is called the scattering of
x-ray.

The scattering of x-ray by atoms is considered to be in two parallel planes. At first,

the two incident rays are in phase with each other ( the maxima and minima occur
at the same position),
The upper wave is scattered or reflected by an atom in the first layer, while the
lower wave is scattered by an atom in the second layer.

In order for these two (2) scattered to be in phase again, the extra distance travelled
by the lower wave must be integral multiple of the wavelength (𝛌) of the x-ray;
The reflection of X-rays from two layers of atoms resulted into the Braggs’
equation Which is given by ; nλ =2dsin𝜃
Where n= 1,2,3…….
λ = wavelength
𝜃 = angles between the x-rays and the plane of the crystal
d = distance between adjacent planes
For the two waves to be in phase again after reflection, it must be true that
2dsin𝜃 = nλ

The reinforced wave produced a dark spot on a photographic film for each value of
𝜃 that satisfies the Braggs equation.
Example 1
X –ray of wavelength 0.154nm strike an Aluminium crystal; the rays are deflected
at an angle of 19.30. Assuming that n=1, calculate the spacing between the planes
of aluminium atoms ( in pm) that is responsible for this angle of deflection ( 1nm
=1000pm). Solution
Using;
2dsin𝜃 = nλ d =

; since n=1 d

=
1000 pm
154nm × 1nm 0.
sin 19.30
d=
d= 233pm
The x-ray diffraction technique offers the most accurate method for determining
bond lengths and bond angles in molecules in the solid state.
Infra-red Spectroscopy
Infra-red spectral arise principally as a result of transition between vibrational
energy level of a molecule. The energy gap between such levels is considerably
less than those involved in visible and ultraviolet spectroscopy, but much greater
than the spacing between the rotational levels.
Consider a diatomic molecule consisting of two different atoms, M 1 and M2; a very
useful model which describe the vibrating motion of such molecule is: a. consisting
of two masses joined by fairly stilt spring
b. if the system is set into vibration in the absence of any frictional force, it will
execute simple
harmonic motion (S.H.M) about an equilibrium position with the two extremest
of the motion
being in contact.

For such a system, the force of vibration about the centre of mass is given by
V
The first constant k is a measure of the strength of bond joining two atoms
together. Practice Question
In a diffractometer, X-rays with a wavelength of 0.1315 nm were used to produce a

diffraction pattern for copper. The first order diffraction (n= 1) occurred at an angle

θ= 25.25°. Determine the spacing between the diffracting planes in copper in pm.

UNIT 4 (Week 8)
 Solid State

Solid-state in Chemistry is the study of the structure, properties and the synthesis of solid
materials. It is also sometimes called as materials chemistry. More significantly, in solid-state
chemistry, we study the concept of a compound in a deeper level. It basically helps us understand
the compound from a molecular level to the crystal structure level.

We are mostly surrounded by solids and we used them more often than liquids and gases. For
different application we need solids widely different properties. Solids generally exhibit certain
characteristics that set them apart from liquids and gases. For example, they have the ability to
resist any force that is applied to its surface. However, the solid-state of compounds largely
depends on the properties of atoms such as their arrangement and the forces acting between
them.

Physical and Chemical Properties of Solids

i. Solids are incompressible, meaning the constituent particle is arranged close to each other
and because of that, there is negligible space between the constituent particle.
ii. Solids are rigid. This is due to lack of space between the constituent particles which make
it rigid or fixed. iii. Solids have definite mass, volume and shape due to which it has a
compact arrangement of constituent particles.
iv. The intermolecular distance between molecules is short. Due to this, the force between
the constituent particles (atoms, molecules or ions) is very strong.
v. The constituents’ particles can only oscillate about their mean positions.

Types of Solid States

Based on the arrangement of constituent particles, solids are classified into two-state types:

1. Crystalline Solids
2. Amorphous Solids

Crystalline Solid State

The term crystal comes from the Greek word “krystallos” which means clear ice.
This term was first applied to the transparent quartz stones, and then the name is
used for solids bounded by many flat, symmetrically arranged faces. A crystalline
solid is that in which the constituent particles are orderly arranged in a
threedimensional pattern called the crystal lattice with uniform intermolecular
forces, and the particles intersect at angles characteristic of the crystal. Examples
include Sodium Chloride, Quartz, Diamond, etc.
Properties of Crystalline Solids

i. Crystalline solids have a sharp melting point and start melting when it reaches a
particular temperature.
ii. The shape of crystalline solids are definite and having typical arrangements of particles.
iii. They show cleavage property i.e. when they are cut with the edge of a sharp tool they
split into two pieces and the newly generated surfaces are smooth and plain. iv. They
have definite heat of fusion (amount of energy needed to melt a given mass of solid at its
melting point).
v. Crystalline solids are anisotropic which means their physical properties like electrical
resistance or refractive index show different values when they are measured along with
different directions in the same crystal.
vi. Crystalline solids are true solids.

Types of Crystalline Solids

On the basis of the nature of intermolecular forces or chemical bonding, crystalline solids are
further classified into four categories. They are,

• Molecular Solids  Ionic solids

• Metallic solids
• Covalent solids

Molecular solids

In molecular solids the constituent particles are molecules. They are further divided into three
categories:

1. Non-Polar Molecular Solids

These solids are formed from molecules or atoms that share a non-polar covalent bond. The
atoms or molecules are held by weak dispersion force or by London forces.
 The physical nature of non-polar solids are soft.
 They don’t conduct electricity so they are
 insulators.  They have a very low melting point. 
Examples: H2, Cl2, I2 etc.

2. Polar Molecular Solids

• These solids are held together by polar covalent bonds and the atoms/molecules are
bonded by relatively stronger dipole-dipole interactions.
• The physical nature is soft and most of these are gases or liquids at room temperature.
• They do not conduct electricity and they have a higher melting point than the non -polar
molecular solids.
• Examples: HCl, SO2, NH3 etc.

3. Hydrogen-Bonded Molecular Solids

The solids contain polar covalent bonds with Hydrogen, Fluorine, Oxygen and Nitrogen atoms.
In these solids, molecules are held together via strong hydrogen bonding.

• The physical nature of such solids are hard.

• They do not conduct electricity.
• The physical state of these solids are volatile liquids or soft solids under room
temperature.
• They have a low melting point.  Examples: H2O (Ice ).

Ionic Solids

In ionic solids the constituent particles are ions. These are formed by the arrangement of cations
and anions by strong Coulombic forces.

• These are hard and brittle in nature.

• Ionic solids act as an insulator in a solid-state but are conductors in a molten and aqueous
state.
• They have a high melting point.
• Example: NaCl, MgO, ZnS, CaF2 etc.

Metallic Solids

• Positive metal ions in a sea of delocalized electrons. These electrons are evenly spread
out throughout the crystal.
• Due to the presence of free and mobile electrons, they are responsible for high electrical
and thermal conductivity.
• They are conductors in both solid and molten state.
• The physical nature of these solids are hard but they are malleable and ductile.
• They have high melting point than ionic solids.
• Examples: Fe, Cu, Ag, Mg, etc.
 Covalent or Network Solids

A wide range of crystalline solids of non-metal form covalent bond between adjacent atoms
throughout the crystal and form a giant molecule or large molecules.

• These solids are hard like diamond and soft like graphite which are isotopes of carbon.
• They are insulators as in the case of a diamond but in case of graphite due to free
electrons, they conduct electricity and act as a conductor.

Amorphous Solid State

Amorphous solid-state comprises of those solids which have the property of rigidity and
incompressibility but to a certain extent. They do not have a definite geometrical form or long
range of order. Examples include glass, rubber, plastic, etc.

Structure of Amorphous Glass

Properties of Amorphous Solids

i. Amorphous solids are gradually softened over a range of temperature and they can be
moulded into different shapes on heating. ii. Amorphous solids are pseudo solids or super
cooled liquids which means they have a tendency to flow very slowly. If you observe that the
glass pans which is fixed to windows of old buildings they are found to be slightly thicker
from the bottom than at the top.
iii. Amorphous solids have irregular shape i.e. their constituent particles do not have definite
geometry of arrangements. iv. When amorphous solids are cut with a sharp edge tool they
form pieces with irregular surfaces.
v. Amorphous solids do not have definite heat of fusion due to its irregular arrangement of the
particles.
vi. Amorphous solids are isotropic in nature which means the value of any physical property
would be same along any direction because of the irregular arrangement of particles.

Uses of Amorphous Solids

Amorphous silicons which is one of the best photovoltaic material converts sunlight into
electricity.
 Summary of Crystalline Verses Amorphous

i. Crystalline solids have a regular three-dimension pattern of ions, atoms or molecules

whereas amorphous solids have a random arrangement of these components
ii. Crystalline solids have an exact melting point whereas amorphous solids melt over a
range of temperature
iii. Amorphous solids yield fragments with irregular patterns when cleaved whereas
crystalline solids depict a definite shape
iv. Crystalline called anisotropic because of different physical properties in all directions
whereas amorphous are called isotropic
v. Examples of amorphous include glass and that of crystalline include diamond.

Isotropy vs Anisotropy

Isotropy means uniformity in all directions. In solid state isotropy means having
identical values of physical properties such as refractive index, electrical
conductance etc., in all directions, whereas anisotropy is the property which
depends on the direction of measurement. Crystalline solids are anisotropic and
they show different values of physical properties when measured along different
directions. The following figure illustrates the anisotropy in crystals due to
different arrangement of their constituents along different directions.
LATTICE ENERGY
This is the energy that brings aggregates of ions in their free gaseous states to form
1 mole of an ionic solid.
Na+(aq) + Cl-(aq) NaCl(s) ∆H =-788kj
The main reason for stability of ionic compound is the attraction between ions of
unlike charges. This attraction of ions together releases energy and cause the ions
to form a solid lattice. The quantitative measure of the stability of any ionic radius
is its lattice energy.
Lattice energy is defined as energy required to completely separate one mole of
solid ionic compound into its aggregate gaseous ions.
Lattice energy cannot be measured directly; however, if we know the structure and
compositions of an ionic compound, we can calculate its lattice energy by using
Coulomb’s law which states that the potential energy , E between to ions is
directly proportional to their charges and inversely proportional to the distance of
separations between them.
1. For a given cation (m+) and anion (X-) separated by distance (d), the potential
energy is given by :

E=
 But E = F × 𝑑
Hence,

F×d =

F
Where 𝑄𝑀+ and 𝑄𝑋− are the charges of (m+) and (X-)
K = Constant
d = distance
The energy is a negative quantity because the formation of one mole of ionic bond
is an exothermic process. Therefore energy must be supply to reverse the process
and it is known as lattice energy (i.e the reversed energy).
The higher the magnititude of the charge, the greater the force of attractive
interaction between the two oppositely charged ions and as the distance between
their centre decreases. Therefore, for a given arrangement of ions, the lattice
energy
increases as the charges on the ions increases as their radii decreases
Practice Question
Arrange in increasing order of lattice energy of the following; NaI, CsI, CaO
Answer
CsI < NaI < CaO

2. Another very important way of calculating lattice energy is by envisaging the

formation of any ionic compound as occurring in a series of well defined steps. We
can then use Hess’s Law to put this steps together in a way that give us the lattice
energy of compound and by so doing we construct a Born- Harber cycle. Henri
Hess a Swiss born in 1840 stating that the heat absorbed or evolved (or the change
in enthalpy) in any chemical reaction is a fixed quantity and is independent of the
path of the reaction or the number of steps taken to obtain the reaction.
Consider the formation of lithium fluoride.
Li(s) + ½ F2(g) LiF(s) , ∆H0F = -594Kjmol-1
Step 1: convert solid Lithium to Lithium vapour
Li(s) Li (g), (∆H0S = 155.2 Kjmol-1) Step
2: Dissociate ½ F2(g) to separate gaseous F atom.
½ F2(g) F (g) (∆H0d = 75.3 Kjmol-1) Step
3: ionize one mole of gaseous lithium atom.
Li(s) Li+ + e- (∆H0I = 520 Kjmol-1)
Step 4: add 1 mole of electron to 1 mole of gaseous F
F(g) + e- F-(g) (∆H0E.A = -328 Kjmol-1)
Step 5: Combine one mole of gaseous Lithium ion and 1 mole of gaseous fluoride
ion
Li+(g) + F-(g) Li F(s)
∆H0f (LiF) = ∆H0S + ∆H0d + ∆H0I.E + ∆H0E.A + ∆H0Lattice
 -594 = 155.2 + 75.3 + 520 - 328) + ∆H0Lattice
∆H0Lattice = -1,016.5 Kjmol-1

(Week 10)

Crystal Lattices and Unit Cells

The ‘crystal lattice’ is the pattern formed by the points and used to represent the positions of
these repeating structural elements. The periodic structure of an ideal crystal is most easily
described by a lattice. The crystal lattice is the array of points at the corners of all the unit cells in
the crystal structure.

What is Crystal Lattice?

The crystal lattice is the symmetrical three-dimensional structural arrangements of atoms, ions
or molecules (constituent particle) inside a crystalline solid as points. It can be defined as the
geometrical arrangement of the atoms, ions or molecules of the crystalline solid as points in
space.
 Characteristics of Crystal Lattice

• In a crystal lattice, each atom, molecule or ions (constituent particle) is represented by a

single point.
• These points are called lattice site or lattice point.
• Lattice sites or points are together joined by a straight line in a crystal lattice.
• When we connect these straight lines we can get a three-dimensional view of the
structure. This 3D arrangement is called Crystal Lattice also known as Bravais Lattices.
Unit Cell

Unit Cell is the smallest part (portion) of a crystal lattice. It is the simplest repeating unit in a
crystal structure. The entire lattice is generated by the repetition of the unit cell in different
directions.

1. Parameters of a Unit Cell

There are six parameters of a unit cell. These are the 3 edges which are a, b, c and the angles
between the edges which are α, β, γ. The edges of a unit cell may be or may not be perpendicular
to each other.

2. Types of Unit Cell

1. Primitive Unit Cells

When the constituent particles occupy only the corner positions, it is known as Primitive Unit
Cells.
2. Centered Unit Cells

When the constituent particles occupy other positions in addition to those at corners, it is known
as Centered Unit Cell. There are 3 types of Centered Unit Cells:

• Body Centered: When the constituent particle at the centre of the body, it is known as
Body Centered Unit cell.
• Face Centered: When the constituent particle present at the centre of each face, it is
known as Face Centered Unit cell.
• End Centered: When the constituent particle present at the centre of two opposite faces,
it is known as an End Centered Unit cell.

Lattice Systems: the 14 Bravais Lattices

Lattices can be classified into "systems", each system being characterized by the shape of its
associated unit cell. In three dimensions, the lattices are categorized into seven crystal lattice
"systems". Within several of these, lattices supporting non-primitive unit cells can be defined.
The classification scheme yields a total of 14 possible lattices (called Bravais lattices).

Axial Lengths Unit Cell

System
and Angles Geometry

Cubic a=b=c, α = β = γ =
90°

Tetragonal a = b ≠ c, α = β = γ= 90°

α=β=
Orthorhombic a ≠ b ≠ c, α = β = γ= 90° a = b = c,

Rhombohedral
γ ≠ 90°
 Hexagonal a = b ≠ c, α = β =
90°, γ = 120°

Monoclinic a ≠ b ≠ c, α = γ =
90°, β ≠ 90°

Triclinic a ≠ b ≠ c, α ≠ β ≠ γ

The lattice symbols used for classification are as follows:

• P : primitive
• B : end-centered on B-face (convention for Monoclinic systems)
• C : end-centered on C-face (convention for Orthorhombic systems)
• I : body-centered
• F : face-centered
• R : rhombohedral primitive

# of
lattices Lattice
System
in symbols
system

Triclinic (Anorthic) 1 P

Monoclinic 2 P, B
P, C, I,
Orthorhombic 4
F
Tetragonal 2 P, I

Isometric (Cubic) 3 P, I, F

Trigonal/Rhombohedral 1 P or R

Hexagonal 1 P
In two dimensions, there are only four possible unit cell shapes and two possible lattice symbols:
Lattice
Cell shape
symbol
General parallelogram P
(rhomboid)
Rectangl p, c
e
Squar P
e
Rhombus with 60 P
degree angle
 Coordination Number and Number of Atoms Per Unit Cell

The number of other particles that each particle in a crystalline solid contacts is known as its
coordination number. Or Coordination Number (CN) is the number of nearest neighbors that
each atom has. In a unit cell, an atom's coordination number is the number of atoms it is touching
For a polonium atom in a simple cubic array, the coordination number is, therefore, six.

Figure 2 . An atom in a simple cubic lattice structure contacts six other atoms, so
it has a coordination number of six.

In a simple cubic lattice, the unit cell that repeats in all directions is a cube defined
by the centers of eight atoms, as shown in Figure 3. Atoms at adjacent corners of
this unit cell contact each other, so the edge length of this cell is equal to two
atomic radii, or one atomic diameter. A cubic unit cell contains only the parts of
these atoms that are within it. Since an atom at a corner of a simple cubic unit cell
is contained by a total of eight unit cells, only one-eighth of that atom is within a
specific unit cell. And since each simple cubic unit cell has one atom at each of its
eight “corners,” there is 8×18=1 atom within one simple cubic unit cell.
 Figure 3. A simple cubic lattice unit cell contains one-eighth of an atom at each of
its eight corners, so it contains one atom total.

Calculation of Atomic Radius and Density for Metals.

Example 1
If the edge length of the unit cell of alpha polonium is 336 pm.

(a) Determine the radius of a polonium atom.

(b) Determine the density of alpha polonium.

Solution
Alpha polonium crystallizes in a simple cubic unit cell:
(a) Two adjacent Po atoms contact each other, so the edge length of this cell is equal to two Po
atomic radii: l = 2r.

Therefore, the radius of Po is

r= =168pm
.
𝑚𝑎𝑠𝑠
(b) Density is given by density = .

The density of polonium can be found by determining the density of its unit cell (the mass
contained within a unit cell divided by the volume of the unit cell). Since a Po unit cell contains
one-eighth of a Po atom at each of its eight corners, a unit cell contains one Po atom.

The mass of a Po unit cell can be found by:

1Po\;unit\;cell × g
The volume of a Po unit cell can be found by:
 V=l3
Where I = edge length = 336pm
100cm = 1012 pm
Xcm = 336pm
X = 336 × 1010cm = I
V=l3 =(336 ×10−10cm)3=3.79×10−23cm3

Therefore, the density of Po = 9.16g/cm3

Example 2
The edge length of the unit cell for nickel is 0.3524 nm. The density of Ni is 8.90 g/cm 3. Does
nickel crystallize in a simple cubic structure? Explain.

Solution

No. If Ni was simple cubic, its density would be given by:

1Ni\;atom × × g
V= l3 = (3.524×10−8cm)3= 4.376×10−23cm3

Then the density of Ni would be =2.23g/cm3

Since the actual density of Ni is not close to this, Ni does not form a simple cubic structure.

Some metals crystallize in an arrangement that has a cubic unit cell with atoms at
all of the corners and an atom in the center, as shown in Figure 4. This is called a
bodycentered cubic (BCC) solid. Atoms in the corners of a BCC unit cell do not
contact each other but contact the atom in the center. A BCC unit cell contains two
atoms: one-eighth of an atom at each of the eight corners ( atom from the
corners) plus one atom from the center. Any atom in this structure touches four
atoms in the layer above it and four atoms in the layer below it. Thus, an atom in a
BCC structure has a coordination number of eight.
Figure 4. In a body-centered cubic structure, atoms in a specific layer do not touch each other.
Each atom touches four atoms in the layer above it and four atoms in the layer below it.

Atoms in BCC arrangements are much more efficiently packed than in a simple cubic structure,
occupying about 68% of the total volume. Isomorphous metals with a BCC structure include K,
Ba, Cr, Mo, W, and Fe at room temperature. (Elements or compounds that crystallize with the
same structure are said to be isomorphous.)

Many other metals, such as aluminum, copper, and lead, crystallize in an arrangement that has a
cubic unit cell with atoms at all of the corners and at the centers of each face, as illustrated in
Figure 5. This arrangement is called a face-centered cubic (FCC) solid. A FCC unit cell
contains four atoms: one-eighth of an atom at each of the eight corners ( =1 atom from
the corners) and one-half of an atom on each of the six faces (6×12=3 atoms from the faces). The
atoms at the corners touch the atoms in the centers of the adjacent faces along the face diagonals
of the cube. Because the atoms are on identical lattice points, they have identical environments.

Figure 5. A face-centered cubic solid has atoms at the corners and, as the name
implies, at the centers of the faces of its unit cells.
Figure 8. A CCP arrangement consists of three repeating layers (ABCABC…) of
hexagonally arranged atoms. Atoms in a CCP structure have a coordination
number of 12 because they contact six atoms in their layer, plus three atoms in the
layer above and three atoms in the layer below. By rotating our perspective, we
can see that a CCP structure has a unit cell with a face containing an atom from
layer A at one corner, atoms from layer B across a diagonal (at two corners and in
the middle of the face), and an atom from layer C at the remaining corner. This is
the same as a face-centered cubic arrangement.

Example 3.

Calcium crystallizes in a face-centered cubic structure. The edge length of its unit
cell is 558.8pm.

(a) What is the atomic radius of Ca in this structure?

(b) Calculate the density of Ca.

Solution

(a) In an FCC structure, Ca atoms contact each other across the

diagonal of the face, so the length of the diagonal is equal to four Ca
atomic radii (d = 4r). Two adjacent edges and the diagonal of the face
form a right triangle, with the length of each side equal to 558.8pm and
the length of the hypotenuse equal to four Ca atomic radii:

a2 + a2 = d2
(558.8pm)2 + (558.5pm)2 = (4r)2 (558.8pm)2
+ (558.5pm)2 = 16r2
r

Solving this gives r= =197.6pmg for a Ca atom

(b) Density is given by density= .

The density of calcium can be found by determining the density of its unit cell: for
example, the mass contained within a unit cell divided by the volume of the unit
cell.
A face-centered Ca unit cell has one-eighth of an atom at each of the eight corners
=1 atom) and one-half of an atom on each of the six faces 6× =3), for a total
of four atoms in the unit cell.
 The mass of the unit cell can be found by:

1Ca\;unit\;cell × × =
2.662×10−22g

The volume of a Ca unit cell can be found by: V= a3

Where a = edge length = 558.5pm

100cm = 1012 pm
Xcm = 558.5pm
X = 558.5 × 1010cm = a
V=a3 =(558.5 ×10−10cm)3=1.745×10−22cm3

Therefore, the density of Ca = 1.53g/cm3

Coordinati Numb %
on Number er of space
Atoms
Unit Cell
Per
Unit
Cell
Simple Unit Cell
 Coordinati Numb %
on Number er of space
Atoms
Unit Cell
Per
Unit
Cell
Simple Unit Cell
6 1 52%

Body-Centered Cubic

8 2 68%

Face-centered Cubic

74.04
12 4
%

Cubic Closest Packed

 12 4
Numb
er of
Coordinati Atoms %
Unit Cell
on Number Per space
Unit
Cell
74.04
%

Hexagonal Closest
Packed

6* (2)
see 74.04
12
note %
below

What Is Polymorphism? (One Compound, Multiple Unit Cell Modifications)

Crystalline materials can be characterized and distinguished according to the structure of their
unit cell. The phenomenon of one chemical species showing more than one possible unit cell
configuration is known as polymorphism. Many crystalline materials can form different
polymorphs in order to minimize their crystal lattice energy under specific thermodynamic
conditions. While the chemical nature remains same, the physical properties (solubility,
dissolution, nucleation & growth kinetics, bioavailability, morphology, and isolation properties)
can vary between polymorphs.

Polymorphysim can be divided into three types : Enantiotropy, Monotropy and

Dynamic allotropy.
1. Enantiotropy: In some cases one polymorphic form (or allotrope) can change into
another at a definite temperature when the two forms have a common vapour pressure.
This temperature is known as the transition temperature. One form is stable above this
temperature and the other form below it. When the change of one form to the other at the
transition temperature is reversible, the phenomenon is called enantiotropy and the
polymorphic forms enantiotropes. For example, rhombic sulphur ( α -Sulphur) on heating
changes to monoclinic sulphur ( β -Sulphur) at 95.6º C (transition temperature). Also,
monoclinic sulphur, on cooling, again changes to rhombic sulphur at 95.6ºC. That is,
95.6°C
α -Sulphur β -Sulphur

Thus α -Sulphur and β -Sulphur are enantiotropic.

2. Monotropy It occurs when one form is stable and the other metastable. The metastable
changes to the stable form at all temperatures and the change is not reversible. Thus there
is no transition temperature as the vapour pressures are never equal. This type of
polymorphism is exhibited by phosphorus,

White phosphorus → Red phosphorus

Crystal defect: is the imperfection in the regular geometrical arrangement of the atoms in a
crystalline solid. These imperfections result from deformation of the solid, rapid cooling from
high temperature, or high-energy radiation (X-rays or neutrons) striking the solid. Located at
single points, along lines, or on whole surfaces in the solid, these defects influence its
mechanical, electrical, and optical behaviour.

Types of crystal defect

1. Point defects: include the Frenkel type, the Schottky type, and the impurity type. The
Frenkel defect involves a single ion, which is displaced from its normal lattice point and
shifts to a nearby interstice, or space, between atoms in the lattice. In the Schottky defect,
two ions of opposite sign leave the lattice. Impurity defects are foreign atoms that replace
some of the atoms making up the solid or that squeeze into the interstices; they are
important in the electrical behaviour of semiconductors, which are materials used in
computer chips and other electronic devices
2. Line defects, or dislocations, are lines along which whole rows of atoms in a solid are
arranged anomalously. The resulting irregularity in spacing is most severe along a line
called the line of dislocation. Line defects can weaken or strengthen solids.
3. Surface defects may arise at the boundary between two grains, or small crystals, within a
larger crystal. The rows of atoms in two different grains may run in slightly different
directions, leading to a mismatch across the grain boundary. The actual external surface of
a crystal is also a surface defect because the atoms on the surface adjust their positions to
accommodate for the absence of neighbouring atoms outside the surface.

Photochemical reaction

A chemical reaction initiated by the absorption of energy in the form of light. The consequence
of molecules’ absorbing light is the creation of transient excited states whose chemical and
physical properties differ greatly from the original molecules. These new chemical species can
fall apart, change to new structures, combine with each other or other molecules, or transfer
electrons, hydrogen atoms, protons, or their electronic excitation energy to other molecules.
Excited states are stronger acids and stronger reductants than the original ground states.

It is this last property that is crucial in the most important of all photochemical processes,
photosynthesis, upon which almost all life on Earth depends. Through photosynthesis, plants
convert the energy of sunlight into stored chemical energy by forming carbohydrates from
atmospheric carbon dioxide and water and releasing molecular oxygen as a byproduct. Both
carbohydrates and oxygen are needed to sustain animal life.
6CO2+ 6HO C6H12O6 + 6O2 + Energy

Many other processes in nature are photochemical for examples;

 i. The ability to see the world starts with a photochemical reaction in the eye, in which retinal,
a molecule in the photoreceptor cell rhodopsin, isomerizes (or changes shape) about a double
bond after absorbing light. ii. Vitamin D, essential for normal bone and teeth development and
kidney function, is formed in the skin of animals after exposure of the chemical 7-
dehydrocholesterol to sunlight.
iii. Ozone protects Earth’s surface from intense, deep ultraviolet (UV) irradiation, which is
damaging to DNA and is formed in the stratosphere by a photochemical dissociation
(separation) of molecular oxygen (O2) into individual oxygen atoms, followed by
subsequent reaction of those oxygen atoms with molecular oxygen to produce ozone (O 3).
UV radiation that does get through the ozone layer photochemically damages DNA, which
in turn introduces mutations on its replication that can lead to skin cancer.

ELECTROCHEMISTRY
Electrochemistry is the branch of physical chemistry concerned with the behavior of ions in
solutions, their interaction with one another and with a metallic conductor (Electrode) and the
subsequent relation between chemical energy and electrical energy.

Uses of Electrochemistry

1. Power source
 a. Batteries
b. Fuel cells (Space craft)
2. Corrosion prevention
3. Pollution analysis
4. Biomedical research

ELECTROLYTIC AND ELECTROCHEMICAL CELLS

Electrolytic Cell
Any device in which electrical energy is converted into chemical energy, e.g. any set-up used in
electrolysis; which comprises of: 1. An electrolyte 2. An electrodes

a. Anode which is the positive electrode

b. Cathode which is the negative electrode
3. Both the electrolyte and the electrode are existing in the same container; with the two
electrodes connected externally by an electric circuit serving as a source of direct current
(DC).

Electrochemical Cell
This is a device that converts chemical energy into electrical energy e.g. batteries. In this type of
cell Anode is the negative electrode while Cathode is the positive electrode. Each
electrode is dipped separately into its electrolyte or a paste containing ions. The two separate
electrolytes are connected (joined) by a salt bridge; which is a paste of KNO3 or KCl.

CELL POTENTIAL
When a metal is in contact with water or ionic solution it dissociates to give ions in the solution
leaving behind electrons on the remaining surface of the metal; e.g.

The force with which these electrons are transported from the negative electrode to the positive
electrode is called electromotive force (EMF) or cell potential having a unit of volts;

Reduction Potential
Generally when a metal electrode is dipped in its aqueous solution, the ions in the
solution try to withdraw electrons from the metal electrode in order to get reduced. The extent
with which this process takes place is referred to as reduction potential.
STANDARD HYDROGEN ELECTRODE (SHE)
The SHE consists of hydrogen gas (H2(g)) at 1atm bubbling over a platinised platinum plate
(electrode) immersed in a solution of 1M HCl at 25°C. The platinised platinum electrode has the
following uses in the SHE:
1. It acts as an inert metal connection to the H2/H+ system.
2. It allows H2(g) to be adsorbed on its surface.
3. Being platinsed, it has increased surface area so that it can establish an equilibrium
between H2(g) and H+(aq) as rapidly as possible.
The SHE is assumed to have a standard electrode potential E°, of zero (0.00V); i.e. for the
reaction ½H2(g) → H+(aq) + e-; E° = 0.00V.

Standard Electrode (Half – Cell) Reduction Potential

To measure the standard reduction potential of a given half-cell;
1. All the ionic species must have a concentration of 1M.
2. All gases should be at 1atm pressure.
3. Working temperature should be 25°C, and
4. Platinum should be used as the electrode when the half-cell does not include a metal.
Generally, the standard reduction potential (E°) of any half – cell is obtained by reference to
that of the SHE. For instance the standard reduction potential of a Zn (s)/Zn2+(aq) half – cell, is
the potential difference between SHE and the zinc half – cell. Generally,
E°cell = E°RHS - E°LHS
= E°Zn/Zn2+ - E°H2/H+
= E°Zn/Zn2+ - 0
E°Zn/Zn2+ = -0.76V

VOLTAIC CELL
This is formed by combining two types of half – cells, e.g. a Daniel cell is formed by combining
zinc and copper half cells.
In this cell the reaction taking place is Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s). The standard
reduction potential of this type of cell is defined as “the reduction potential for the substance that
actually undergoes reduction minus the reduction potential for the substance that is
forced to undergo oxidation”. Thus;
CELL DIAGRAM
A cell diagram is any representation that shows the nature of the electrode material,
nature of the solution in contact with the electrode, which half – cell is anode or cathode and the
reactants or products in each half cell.
To draw a cell diagram one needs to:
1. Identify the anode half – cell (Oxidation half – cell) i.e. the half – cell with smaller or
more negative E° value. Also to identify the cathode (reduction half – cell) i.e. the
half – cell with larger E° value.
2. The salt bridge is represented by a pair of vertical lines or single broken line which
separates the two half – cells.
3. A single vertical line is used to represent a phase boundary with the
concentration of the Mn+(aq) shown in brackets ( ).

4. If inert electrodes are used, the least oxidized specie is written next to it. Thus, the
cell diagram for Daniel cell is;

Similarly, the cell diagram for standard Zn electrode is;

While example of a least oxidized specie with inert electrode is;

ELECTROCHEMICAL SERIES
This is a series showing the arrangement of electrodes half – cell reactions and their
corresponding standard reduction potential, E°(V) in their decreasing or increasing order.

Uses of Reduction Potential

1. Oxidising Agent/Oxidising Power

A positive value of E° implies that the corresponding electrode has tendency to
gain electrons; and the more the positive the E°, the greater the tendency of the electrode
to gain electron. Thus, any half – cell with positive E° value is an oxidizing agent, and
the oxidizing power increases with increase in the E° value.

2. Spontaneous Redox Reaction

A reaction is spontaneous if and only if E°cell is positive.
EXAMPLE
Assuming the reaction Fe2+(aq) + Ni(s) → Fe(s) + Ni2+(aq). The two half – cells are:
Reduction half – cell; Fe2+(aq) + 2e- → Fe(s) having E° = -0.44V.
 Oxidation half – cell; Ni(s) → Ni2+(aq) + 2e- having E° = +0.25V [NOTE: E° for
oxidation
= - E° for 0.19V; and
reduction i.e. from
therefore the reaction is non-spontaneous.
EXERCISE
A mixture contains Cr3+(aq) and Zn2+(aq). Deduce the overall cell reaction and calculate E°cell.
3. Determination of the Direction of a given Reaction Recalling that for the reaction; Fe 2+
(aq)+ Ni(s) → Fe(s) + Ni2+(aq) the cell potential (E°cell) is -0.19V which implies that the
reaction is non – spontaneous. However, for the reaction;
Fe(s) + Ni2+(aq) → Fe2+(aq) + Ni(s)
The half – reactions are:
Oxidation half – reaction: Fe(s) → Fe2+(aq) + 2e- Reduction half
– reaction: Ni2+ + 2e- → Ni
E°cell
Thus, changing the direction of the reaction made it to become spontaneous.
4. Possible Half – Reaction Combination
• If the electrochemical series is arranged in an increasing order, then any specie
on the LHS of a given half – reaction will react spontaneously with another specie on
the
RHS of a given half – reaction located above it. E.g.
Ca2+/Ca: Ca2+ + 2e- → Ca: E° = -2.87V
Na+/Na: Na+ + e- → Na: E° = -2.71V This
shows that Na+ can combine with Ca.
• If the electrochemical series is in decreasing order, then a specie on the LHS
combines with any specie on the RHS of a half reaction below it.
5. Preferential Discharge of Ions in Electrolysis
The more positive the E° of an ion in the electrochemical series, the more preferentially it
is discharged during electrolysis. E.g. in electrolysis of aqueous Cu 2+ (i.e. Cu2+ & H2O) Cu(s)
is deposited but not H2O, this is because Cu2+/Cu electrode has E° = +0.34V, while H 2O/H2
electrode has E° = -0.83V. However, in electrolysis of aqueous Al 3+, water is discharged but
not Al(s) which has E° = -1.66V.

Reduction Potential in Non – Standard State (E) For

any given reaction of the type: aA + bB → cC +
dD

; where n is number of electrons transferred while

Q is reaction
quotient defined by
 ; and if T = 25°C, ; thus

INTRODUCTION TO NUCLEAR CHEMISTRY

The nucleus of every atom of all elements, except hydrogen, contains both protons
and neutrons (the word nucleus is a general term also used to describe protons and
neutrons). In the nucleus, the neutrons appear to act as a kind of nuclear glue by
overcoming the proton – proton repulsion which can cause the nucleus to
disintegrate.
Mass defect
It has been found that there is a difference between the mass of the nucleus of an
element and the sum of the masses (of proton and neutrons) in the nucleus of an
atom.
For example, the mass of 4He nucleus is 4.00150 amu. However, the two protons
and two neutrons combined have a different mass, thus;
Mass of 2 protons = 2×1.00728 amu = 2.01456 amu
Mass of 2 neutrons = 2×1.00867amu = 2.01734 amu
Total mass of nucleus = 4.03190 amu

∆M (4.03190 + 4.00150)amu = 0.03040 amu

The loss of mass that occurs when protons and neutrons combine to form a
nucleus is called the Mass defect of the nucleus. The lost mass does not simply
disappear; it is converted into energy. It is this energy that holds the nucleus
together and gives it the stability so that the nucleus does not disintegrate. Nuclear
binding energy can be defined as the energy required to break up a nucleus into its
component parts (i.e. protons and neutrons).
Nuclear Stability
The principal factor for determining the nuclear stability is the neutron to proton
ratio (n:p). For a stable atom with low atomic number, the n:p value is close to 1.
As the atomic number increases, the n: p ratios of the stable nuclei becomes greater
than 1. This deviation occurs because higher atomic number (in the nucleus of an
atom) requires large number of neutrons to stabilize it. This stabilization is
achieved by counteracting the strong repulsion amongst the protons in the nucleus.
In the graph that follows a plot of the number of neutrons versus the number of
protons in various atoms is shown. The stable nuclei are located in an area of the
graph known as the “belt of stability”. Most of the radioactive nuclei lie outside
this belt.
If the n:p ratio is either too high or too low the nuclei tend be unstable and will
tend to split to give smaller nuclei. This is called NUCLEAR FISSION. When
nuclei divide a high energy radiation and sometimes sub–atomic particles are
emitted from the atom, and this emission of smaller particles and energy is called
radioactivity. Radioactivity can therefore be defined as the spontaneous emission
of particles and/or radiation from the nucleus of an atom. The process is called
radioactive decay.
Radioactivity was first discovered by a German scientist called „‟Wilhelm
Roentgen‟‟ in 1895.
Types of Radioactivity
There are two types of radioactivity; Natural radioactivity and Artificial
radioactivity.
 NATURAL RADIOACTIVITY
Some minerals or elements naturally emit radiation and particles: this phenomena
was observed by Ernest Rutherford to be of three types (α, β and γ). In an
experiment in which he passed a beam of radiation from a radioactive source
through a slit, then through electrically charged plates unto a photographic plate, he
found that the beam had split into three components. The component that was

attracted towards the positive plate he called beta (β) particles, the one towards the
negative plate alpha (α) particles, and the one not affected by the charge, gamma
(γ)
radiation.

PHOTOGRAPHIC
PLATE

β
LEAD BLOCK + ve plate

α
- ve plate
RADIOACTIVE
SUBSTANCE

BEHAVIOUR OF RADIATION FROM A RADIOACTIVE SOURCE IN AN

ELECTRIC FIELD

ALPHA PARTICLES
 This is a Helium nucleus with a mass of 4 amu and a +2 charge (He2+).
 It normally has a high velocity, 1/20 of the speed of light and it is emitted
from the nuclei of heavier unstable isotopes.
  It is highly ionizing as it attracts electrons to form Helium gas. This makes
it to have low penetrating power in the air.
 They travel only short distances in the air (4 to 5 cm).
 Compared to β – particles and γ-radiation, α- particles have relatively low
speed and are involved in frequent collisions with other atoms, which
causes them to be stopped easily, even by a sheet of paper.
 α- Particles travel in straight lines.
When heavy unstable elements split to give another element together with -

particles, the decay is called alpha decay and the mass of the decaying element
decreases by four while the atomic number decreases by two, in addition to the high
energy γ- radiation. E.g.
224
𝑅𝑎 220
𝑅𝑎
86 +
4
2𝐻𝑒 + γ
88

BETA PARTICLES
 These are fast moving electrons which travel almost at the speed of light.
 They are negatively charged and have practically no mass and are ejected
from unstable nuclei in what is called a beta decay.
 β – Particles do not have much penetrating power, but are more penetrating
than - particles. They need a thin sheet of aluminum of some few
millimeters thickness to be stopped, compared to a piece of paper for α -
particles.
 β – particles meander in the air due to their very tiny masses, as can be seen
in a cloud chamber experiment, compared to α - particles that are heavier
and go in a straight line.
The loss of β– particles by an unstable isotope is called beta decay. Here,
one of the neutrons, which are neutral, looses an electron to form a positive proton
and an electron is emitted.

An example of β – decay is:

234
90𝑇ℎ
 GAMMA RADIATION
 This is a high energy electromagnetic radiation that accompanies both α –
and β decays and is emitted by nuclei with excess energy. γ - radiation is
not a particle.
 γ- Radiation is of very short wavelength with an extremely high penetrating
power. It needs very thick Lead or a block of concrete to stop it.
 γ - Radiation travels at the speed of light and has no charge or mass.

POSITRION EMISSION AND ELECTRON CAPTURE

There are two other types of radioactive decay processes that occur, in addition to ,
β, and γ - radiations.
1) Positron emission is when a proton in the nucleus is converted into a neutron and in
the process a positron is ejected (10e). A positron is the exact opposite of an electron
in terms of charge (+ ve) but has the same mass. When a positron is ejected, a
decrease in the atomic number is observed since the proton is converted to a
neutron.
There is however no change in mass number. For example

2) When a proton in the nucleus captures an inner shell electron and is thereby
converted to a neutron, the process is called electron capture. Here also, the atomic
number decreases by one, since a proton is converted to a neutron, but the mass
number remains unchanged.

A summary of radioactive decay process is shown below:

process Symbol Change in Change in mass Change in
atomic no no neutron no
 4
α - Emission β 𝐻𝑒 -2 -4 -2
2
β – Emission 0𝑒
+1 0 -1
−1

γ – Emission o 0 0 0

oγ
Positron Emission -1 0 +1
Electron Capture o -1 0 +1
e
1

E.C

Nuclear reaction can occur naturally through spontaneous decays of

unstable nuclei. Unstable nuclei can continue to decay to form new elements until a

last stable one is formed. When an element that has a very large nucleus like 238

92

decays into a series of elements until at last a stable final element is formed, the

process is called a decay series. Below is an example of radioactive decay series.

238
The above sequence is by both α - and β – decays. It is  radioactive decay
series.
 ARTIFICIAL NUCLEAR REACTIONS
Artificial nuclear reactions occur when certain stable nuclei is bombarded with α -

particles, β – particles, neutrons, protons (11H ) or deuterium (21H ). These

reactions are non – spontaneous since they need to be brought about by external
forces. The formation of new elements through this process of bombardment
reaction is called nuclear transmutation. A lot of elements have been formed
through this process. In fact, all elements with atomic numbers higher than
uranium (92) are formed through this process. Examples of artificial nuclear
reactions include:

14
7 N+24He→817O+11H

Even though new elements are formed; we must note that the sum of the mass
numbers and the sum of the atomic numbers before and after the nuclear reactions
are conserved. Radioactive Half-life
Law of Radioactive Decay

When a radioactive material undergoes α, β or γ-decay, the number of nuclei undergoing the decay, per
unit time, is proportional to the total number of nuclei in the sample material. So,

If N = total number of nuclei in the sample and ΔN = number of nuclei that undergo decay in time Δt then,

ΔN/ Δt N

Or, ΔN/ Δt = λN … (1)

where λ = radioactive decay constant or disintegration constant. Now, the change in the number of nuclei
in the sample is, dN = – ΔN in time Δt. Hence, the rate of change of N (in the limit Δt → 0) is,

dN/dt = – λN

Or, dN/N = – λ dt

Now, integrating both the sides of the above equation, we get,

 N
N0∫ dN/N = λ tt0∫ dt … (2)

Or, ln N – ln N0 = – λ (t – t0) … (3)

Where, N0 is the number of radioactive nuclei in the sample at some arbitrary time t 0 and N is the number
of radioactive nuclei at any subsequent time t. Next, we set t0 = 0 and rearrange the above equation (3) to
get,

ln (N/N0) = – λt Or,

N(t) = N0e– λt … (4)

Equation (4) is the Law of Radioactive Decay.

The Decay Rate

In radioactivity calculations, we are more interested in the decay rate R ( = – dN/dt) than in N itself. This
rate gives us the number of nuclei decaying per unit time. Even if we don’t know the number of nuclei in
the sample, by simply measuring the number of emissions of α, β or γ particles in 10 or 20 seconds, we
can calculate the decay rate. Let’s say that we consider a time interval dt and get a decay count ΔN (= –
dN). The decay rate is now defined as,

R = – dN/dt

Differentiating equation (4) on both sides, we get,

R = λ N0 e−λt

Or, R = R0e−λt … (5)

Where, R0 is the radioactive decay rate at the time t = 0, and R is the rate at any subsequent time t.
Equation
(5) is the alternative form of the Law of Radioactive Decay. Now we can rewrite equation (1) as follows,

R = λN … (6)

where R and the number of radioactive nuclei that have not yet undergone decay must be evaluated at the
same instant.

Half-Life and Mean Life

The total decay rate of a sample is also known as the activity of the sample. The SI unit
for measurement of activity is ‘becquerel’ and is defined as,

1 becquerel = 1 Bq = 1 decay per second

An older unit, the curie, is still in common use:

1 curie = 1 Ci = 3.7 × 1010 Bq (decays per second)

There are two ways to measure the time for which a radionuclide can last.

• Half-life T1/2 – the time at which both R and N are reduced to half of their initial values

• Mean life τ – the time at which both R and N have been reduced to, e-1 of their initial values.
Calculating Half-Life

Let’s find the relation between T1/2 and the disintegration constant λ. For this, let’s input the following
values in equation (5),

R = (1/2)R0 and t = T1/2

So, we get T1/2 = (ln2)/ λ

Or, T1/2 = 0.693/ λ … (7)

Calculating Mean life

Next, let’s find the relation between the mean life τ and the disintegration constant λ. For this, let’s
consider equation (5),

• The number of nuclei which decay in the time interval: ‘t’ to ‘t + Δt’ is: R(t)Δt = (λN 0e–λt Δt).

• Each of them has lived for time ‘t’.

• Hence, the total life of all these nuclei is tλN0e–λt Δt

Hence, to obtain the mean life, we integrate this expression over all the times from 0 to ∞ and divide by
the total number of nuclei at t = 0 (which is N0).

τ = (λN0 0∞∫ te–λtdt)/N0

= λ0∞∫ te–λtdt
On solving this integral, we get

τ = 1/λ

Therefore, we can summarise the observations as follows:

T1/2 = (ln2)/λ = τ ln 2 … (8)

Solved Examples for You

Question: The half-life of 23892U undergoing α-decay is 4.5 × 109 years. What is the activity of 1g
sample of 23892U ?

Answer: T1/2 = 4.5 x 109 years = 4.5 x 109years x 3.6 x 107 seconds/year = 1.42 x 1017 seconds

We know that 1 k mol of any isotope contains Avogadro’s number of atoms. Hence, 1g of 23892U contains,
{1/(238 x 10-3)} x 6.025 x 1026 = 25.3 x 1020 atoms. Therefore, the decay rate R is,

R = λN
= (0.693/T1/2)N
= (0.693 x 25.3 x 1020) / (1.42 x 1017)

Therefore, R = 1.23 x 104 Bq

APPLICATIONS OF RADIOACTIVITY
There are many good uses for radioactive isotopes if handled properly. Otherwise,
they can be very harmful biologically.
1. Controlled application of radioisotopes used include Iodine- 131, Cobalt –
60, Cesium – 137 for disease treatment e.g. cancer, etc.
2. Medical equipments like surgical equipments are sterilized using radiation.
Food is also preserved by radiation with γ – rays.
3. Radioisotopes are used as tracers where they detect leaks in water pipes or
oil pipelines. A Geiger – Muller counter can detect where the radiation is
leaking thereby avoiding the uprooting of the whole pipeline.