Chapter Five

The Electronic Structure of Atom

Electromagnetic Radiation
 Electromagnetic radiation is a radiation that
comes from the sun.
 Why it is called electromagnetic radiation
because it contains both magnetic and electric
fields that are perpendicular to each other.
 It travels at a speed of 3.0 10 8 m/s.
 Example the light energy that is used in
microwave oven, x-ray used by doctors
 Light has dual nature. Namely: wave nature
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Properties of Waves
Waves are characterized by:
a)wavelength
b) frequency
c) Speed
d) amplitude
e) wave number
a) Wavelength
Wavelength is the distance between two adjacent troughs or crests.
b) Frequency
It is the number of complete oscillations per unit time.
C) Speed
All electromagnetic radiations travel at a speed of 3.0 108 m/s.
d) Amplitude
It is the maximum displacement from the equilibrium position.

2 2
 Amplitude (intensity) of waves
e)

Amplitude (intensity) of waves

Wave number,
Wave number is the reciprocal of wavelength.
=
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 =
where = wavelength, C = speed of light and wavelength
It is also given in nm (1 nm = 10-9 m) and in Angstroms (Å)
(1 Å = 10-10 m).
The unit of frequency is s1 or 1/s
It is also called “hertz’’ (Hz).

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Example: When green light is emitted from an oxygen atom it
has a wavelength of 558 nm. What is the frequency?
=
5.38 Hz

Planck’s Constant
Energy is quantized and it occurs only in discrete units.
=
Where, is change in energy (J)
h is Planck’s constant = 6.626 10-34 JS
is frequency () and is wavelength (m)

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Example: Blue color in fireworks is often achieved by heating copper
(I) chloride (CuCl) to about 1200oC. Then the compound emits blue
light having a wavelength of 450 nm. What is the increment of energy
(the quantum) that is emitted at 4.50 x 102 nm by CuCl?
The quantum of energy can be calculate from the equation
E = h
The frequency  for this case can be calculated as follows:
= = = 6.7 1014 Hz
h = 6.626 10-34 Js 6.7 1014
= 4.44 10-19 J
A sample of CuCl emitting light at 450 nm can only lose energy in
increments of 4.41 x 10-19J.

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 Energy and Mass
According to Einstein theory of relativity,
energy has mass. Einstein equation,
E = mc2 where, E = energy, m = mass
c = speed of light
After rearranging the equation, m =
Now it is possible to calculate the mass that is associated
with a given quantity of energy.
Einstein suggested that electromagnetic radiation can be
viewed as a stream of “particles” called photons. The
energy of each photon is given by,

=h= = = =
It was Einstein who has realized that light could not be
explained completely as waves but it has particle properties
as well. This is called the dual nature of light.
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 Wavelength and Mass
de Broglie thought that if waves like light could have
particle properties that particles like electrons could have
wave properties. We have,
m= m = where = velocity

= de Broglie equation
 = wavelength (m), m = mass (kg),  = velocity (m/s)
h = Planck’s constant, 6.626  1034 J s = kg m2 s1
This equation allows us to calculate the wavelength of a
particle. Matter exhibits both particulate and wave
properties.

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 Example: Compare the wavelength of an electron (mass
= 9.11 x 10-31 kg) traveling at a speed of 1.0 x 107 m/s with
that of a ball (mass = 0.10 kg) traveling at 35 m/s.
We use the equation  = h/m, where
h = 6.626  1034 J.s or 6.626  1034 kg m2 /s
since, 1 J = 1 kg. m2 /s2

For an electron = = =
7.2 m
For the ball
= = = 1.89 m

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 The Photoelectric Effect
Photoelectric effect is the ejection of an electron from the
surface of a metal when light is shone on it.
It was explained by Albert Einstein.
Light is composed of particles called photons.
= + Where is work function and is kinetic energy of an
electron.
= h is minimum frequency or threshold frequency.
=hh=h+ =h-h
=h(-)
= h( - ) Where is maximum wavelength.

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Example:
1)Calculate the energy in joule of
a) photon with a wavelength of 5.0
b) photon with a wavelength of 5.0
2) The photoelectric effect of mercury is observed when the
energy of a photon is not less than 7.25 J.
a) What is the maximum wavelength of light that causes
mercury to exhibit photoelectric effect?
b) If ultraviolet radiation of wavelength 250.0 nm is shone on
the surface of mercury metal, then what will be the kinetic
energy of the ejected electron?
Answer:
1) a) E = h = = = 3.98 J
b) E = h = = = 3.98 J

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 2) = h = = = 7.25 J

= = 274 nm
Atomic Spectra of Hydrogen

When H2 molecules absorb energy, some of the H-H bonds are

broken and this results in excitation of hydrogen atoms.
The excess energy is released by emitting light of various
wavelengths to produce the emission spectrum of hydrogen
atom.
There are two types of Spectra
Continuous spectrum: Contains all the wavelengths of light
in the region. For example when white light passes through
prism, it will be scattered in to seven colours. This is an
example of continuous spectra. There is no space between the
colours.
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a. Line (discrete) spectrum: Contains only some of the
wavelengths of light. Only certain energies are allowed, i.e., the
energy of the electron in the hydrogen atom is quantized.

Line Spectra is divided in to two.

a) absorption Spectra
b) Emission Spectra
When sample absorbs energy, then it will be energized or
excited. Some of the lights are absorbed and some of the
lights will be passed through the sample without
absorption.

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 =h=

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Limitations/ weaknesses of Rutherford’s Atomic Model
1)Rutherford says that the electron in a hydrogen atom spins
around the nucleus as planets do around the sun. i.e, the electron
can have any energy. The electron loses its energy and finally it
will collide with nucleus consequently the atom will collapse.
This implies that an atom is not stable.
2) Rutherford atomic model doesn’t explain line spectra of
hydrogen
Postulates of Bohr
1)The energy of electron of hydrogen atom is quantized meaning
it absorbs or emits discrete amount of energy.
2) The electron in a hydrogen atom is allowed to spin around the
nucleus only in a certain fixed path called orbit or energy level.
3) The electron in a hydrogen atom neither absorbs nor emits
energy as long as it is in one of these orbits. When it is stationary.
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Bohr Radius
Radius of Hydrogen Atom
The radius of each energy level of hydrogen atom
can be calculated using the following formula.
r = Where Bohr radius = 0.53 n = 1,2,3…and ‘r’ is radius
Exercises
Calculate r at n = 1,2,3 and 4
Solution When n= 1
r = = 0.53 = 0.53 m = 5.3 m
when n=2, r = = 0.53 = 0.53 4 = 2.12
= 2.12 m When n = 3, r = = 0.53
0.53 9 = 4.77 = 4.77 m
When n = 4, r = = 0.53 = 0.53 = 0.53 16
= 8.48 m

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 Bohr Energy of Electron in a Hydrogen Atom
The electron in a hydrogen atom spins around the nucleus
only in certain allowed circular orbits. The energy levels
available to the hydrogen atom:
E=
Where E = energy of the levels in the H-atom
A = Bohr energy constant = 2.18 J
n = an integer, the larger the value of n, the larger is
the radius of the orbit.
Bohr was able to calculate energy levels of hydrogen atom
that agree exactly with the experimental value. The
negative sign in the above equation indicates that the
energy which binds the electron to the nucleus is lower
than the energy if the electron was at an infinite distance
from the nucleus.
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Ground State: The lowest possible energy state for an atom
(n = 1).
Energy Changes in the Hydrogen Atom
E = Efinal state  Einitial state

= -2.178 x 10-18J[ -
The wavelength of absorbed or emitted photon can be
calculated from the equation, =

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Example: Calculate the energy that is required to
excite an electron of hydrogen atom from energy
level n = 1 to energy level n = 2. Calculate the
wavelength of light that must be absorbed by an
electron of hydrogen atom to promote from its
ground state to the energy level, n=2 as well.
Using Equation, A( - )
2.18 J ( ) = 2.18 J 0.75 = 1.64 J

= = = 121.2 nm.

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Bohr Line Spectra of the Hydrogen Atom
Hydrogen has the simplest line spectra.
Because hydrogen has only one electron.
Line spectra are used as fingerprint.
Line spectra are characteristics of elements.
Every element has its own line spectra.
It is used to identify elements.
The line spectra of one element is different from the line spectra of
another element because they have different number of electrons.
Balmer formula
Balmer calculated the four lines of hydrogen in the visible region
using an empirical formula.
= ( - ) Where n= 2,3,4,5…, = Rydberg constant
= 1.097 nm
Where n is higher energy orbit and ‘m’ is lower energy orbit.
Calculate the wavelength at n=3, n=4, n=5 and n=6
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= R ( ) when n =3
= R ( ) = R ()
= = cm = 656.5 nm green color.
When n= 4 = R ( ) = R ()
= = cm = 486 nm
When n= 5 = R ( ) = R ()
= = = cm = 434.2 nm
Later on other regions were discovered in the Uv and IR regions.

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 When an electron is dropped from higher energy level to n =1, then it
emits ultraviolet radiation. It is called Lyman series and the region is
called ultraviolet region.
 When an electron is dropped from higher energy level to n = 2, then it
emits visible radiation and the region is said to be visible region. This
series is said to be Balmer series.
 When an electron is dropped from higher energy level to n = 3, then it
emits infrared radiation and the region is said to be infrared region.
This series is known as infrared region.
 When an electron is dropped from higher energy level to n=4, then it
emits infrared radiation and the region is said to be infrared region.
This series is said to be Brackett series.
 When an electron is dropped from higher energy level to n =5, then it
emits infrared radiation and the region is said to be infrared region.
This series is known as Pfund series.
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The first line in Lyman series is 2.
The fourth line in Brackett series is 8.
The third line in Paschen series is 6.
Example: For the second line in Lyman series of the hydrogen
atom, calculate its:
a) wavelength
b) frequency
c) energy
d) energy (Kj/mol)
Solution
a) = R ( ) = R ( ) = R ()
= = 103 nm

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b) = = = 2.91 Hz
c) E = h = 6.63 Js 2.91
E = 1.929 J
1 H = 1.929 J
1 mol = x
x= =
11.612 J/mol = 11.612 KJ/mol

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• The Bohr Atomic Model
As per Bohr electron in a hydrogen atom spins around
the nucleus only in a certain circular path called orbit
or energy level.

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• Merits and Demerits of Bohr Atomic Model
• Merits (advantages) of Bohr Atomic Model
 He was able to explain the line spectra of hydrogen atom.
 He explained the stability of atoms.
Limitations/ weaknesses
• It works only for hydrogen atom.
• It doesn’t have chemical bond formation.
The Quantum Mechanical Model
 This the atomic model that is being used currently.
 It is developed by Erwin Schrodinger.
 He adopted de Broglie’s wave particle duality and
Heisenberg uncertainty principle.

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• de Broglie wave- particle Duality
 It states that a particle of mass ‘m’ and speed ‘v’ has an
associated wavelength,
 = =
Where = wavelength, h = Planck’s constant, p = momentum.
 An object whose mass is very large mass has negligible
wavelength.
Exercise:
1) What is the de Broglie wavelength of an electron with a
velocity of 5.97 m/s ? M(e) = 9.11 Kg.
2) What is the wavelength that is associated with 70.0 Kg person
moving at a speed of 1 m/s ?

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Answer:
1) Given
V= 5.97 m/s, m = 9.11 Kg
Required:
Solution: = = = 0.01219 nm
2) Given:
m = 70 Kg v = 1m/s
Required: = ?
Solution:
= = = 9.471 m

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 An object whose mass is very large has negligible
wavelength as compared with an object whose mass is
negligible ( It has relatively large wavelength).
 The wave nature of an electron should be considered but the
wave nature of a person is negligible because it is very
small and difficult to measure.
Relationship between wavelength, and energy, E
E = h = but = E = = ---------eqn1
Energy and wavelength are inversely related. E
Relationship between energy and momentum
= = Combining the two equations. =

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 E = pc p = m E = m but = c
E = m2 This equation is known as Einstein’s equation.
Heisenberg Uncertainty Principle
 It states that it is impossible to know simultaneously both
the exact position and the exact momentum of a small
particle like an electron.
 The more accurately we know the position of the particle,
the less accurately we can know the momentum of the
particle.
+ + ( E v (x,y), (x,y)) = 0
 The above equation is known as Schrodinger equation.
Where (psi) is wave function and is probability of finding an
electron in a certain region.
 The solutions for Schrodinger equations are quantum 36
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Quantum Numbers
 When Schrodinger equation is solved several wave
functions (orbitals) that satisfy it will be found.
 Each of these orbitals is characterized by a series of
numbers called quantum numbers, which describe various
properties of the orbital.
 There are four types of quantum numbers.
1. The principal quantum number, n
n = 1,2,3 …
It describes the size and energy of an orbital.
2. Azimuthal quantum number (Angular momentum quantum
number), l
It determines the shape of orbital. When l =0 it is s orbital,
When l =1 then it is p orbital, when l =2, then it is d orbital
and when l = 3 then it is f orbital.
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The value of l ranges from 0 to n 1.
l = 0, 1, 2, 3, …n 1
3. Magnetic Quantum Number, ml
 Magnetic quantum number determines the orientation of
orbitals in space.
 The value of ml is determined by l.
 It ranges from l to +l. ml = -l to l
When n = 1 l =0 and ml = 0
When n =2, l = 0,1 and ml = 0, -1,0, 1
When n =3, l = 0,1,2
When l = 0, then it is s orbital. When l =1, then it is p orbital.
When n = 2, then it is d orbital.

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Value of n Allowed Allowed value Subshell Number of Maximu
value of l of ml distribution orbitals m NO of
electrons

1 0 0 1s 1 2
2 0 0 2s 4 8
1 -1 0 +1 2p
3 0 0 3s 9 18
1 -1 0 +1 3p
2 -2 -1 0 +1 +2 3d
4 0 0 4s 16 32
1 -1 0 +1 4p
2 -2 -1 0 +1 +2 4d
3 4f

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 Maximum number of electrons can be calculated using the
formula 2n2 and number of orbitals can be obtained by n 2
4) Magnetic Quantum Number, Ms
 It explains the spinning(rotation) of electron.
 Rotation can be clockwise or anticlockwise.
Shapes of Orbitals
 The shape of s-subshell is spherical.
 The shape of p-subshell is dumbbell.
 The shape of d-subshell is double dumbbell.

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 The three p orbitals

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 The five d- orbitals

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• P-orbitals have three lobes.
• Except for dz2 all the d-orbitals have double dumbbell shape.
• Except for dz2 all the d-orbitals have four lobes.
• Node is the region where the probability of finding an
electron is zero.
• Anti-node is the region where the probability of finding an
electron is maximum.
• Electronic Configuration
 Electronic configuration is the distribution of electrons
among the available orbitals in an atom.

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Example: Write the electronic configuration of chlorine using
a. Subshell.
b. Noble gas as a core.
c. Main shell.
d. Tell to which group and period does this element belong.
Answer: 1s2 2s2 2p6 3s2 3p
b) [Ne] 3s2 3p
c) 2, 8, 7 K, L, M
d) group: III A Period = 7
Group number corresponds to the largest principal quantum number
whereas period corresponds to the electrons on this quantum number.
Write the electronic configuration of
Mg, Ca, Fe, Cr and Cu using
e. Subshell.
Noble gas as a core.
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o Rules governing the electronic configuration
a. The Aufbau Principle(building up Principle)
It states that the available orbitals should be filled with
electrons starting from the lowest energy level.
b. The Hund’s Rule(the bus seat rule)
It states that electrons occupy degenerate orbitals singly with
parallel spin before they are paired up.
e.g 1s2 2s2 2p3
1s2 2s2 2p3
c. The Pauli Exclusion Principle
It states that no two electrons in an atom can have four similar
quantum numbers.

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• n, l, ml, ms
• The maximum capacity of an orbital is two
electrons.
1 n l ml ms
1 0 0
1 0 0

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