Chapter 2:

Atomic structure

2.1 Bohr’s Atomic Model

2.2 Quantum Mechanical Model
2.3 Electronic Configuration

1
 INTRODUCTION

Matter is composed Atoms A very large Electrons Electrons

of tiny indivisible consist of volume move around occupy
particles called large sphere around the nucleus in orbitals.
atoms. embedded +vely charge fixed orbit.
with smaller nucleus in
–vely charge which
particles. electrons
2
move.
2.1 Bohr’s Atomic Model

3
 Learning Outcome
i. Describe Bohr’s atomic model
ii. Explain the existence of energy levels in an atom
iii. Calculate the energy of an electron at particular
level
iv. Describe the formation of line spectrum of
hydrogen atom
v. Illustrate the formation of Lyman, Balmer,
Paschen, Brackett and Pfund series
vi. Calculate the energy change of an electron during
transition 4
 Learning Outcome
i. Calculate the photon of energy emitted by an
electron that produces a particular wavelength
during transition.
ii. Perform calculations involving the Rydberg
equation
iii. Calculate ionisation energy of hydrogen atom
from Lyman series
iv. State the limitation of Bohr’s atomic model
v. State the dual nature of electron using de
Broglie’s postulate and Heisenberg’s uncertainty
principle 5
 Bohr based his model on the
following postulates:
First Postulates
 Electron moves in circular orbits
around the nucleus.
 While moving in the orbit, the
electron does not radiate or
absorb any energy.

[orbit = energy level=shell]

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 Orbit:
is a pathway where the electron is move
around the nucleus.

Orbit

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Second Postulate
 The moving electron has a
specific amount of energy; its
energy is quantised.

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 How to calculate the energy?
 The energy of an electron in its energy level is given by:
1
En  R H  2 
n 
RH (Rydberg constant) = 2.18 x 10-18J.
n (principal quantum number) = 1, 2, 3 …. ∞ (integer)
 Note:
 n identifies the orbit of electron
 Energy is zero if electron is located infinitely far from nucleus.

9
 Energy of an electron is quantized , it
has a specific value
Electron orbiting the
nucleus at n=1 has
the energy of E1 = -RH
12

e
nucleus

n=1
If an electron occupies
n=4, it has the energy of:
E4= -RH n=2
n=3
42
n=4

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Example

Calculate the energy of an electron in the second

energy level of a hydrogen atom.

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Third postulate
 Energy is emitted or absorbed by an electron as it changes

from one allowed energy level to another.

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• At ordinary conditions, the electron is at the ground
state.
• If energy is supplied, electron absorbed the energy
and is promoted from a lower energy level to a
higher energy level. (Electron is excited).
 Electron at its excited state is unstable.

 It will fall back to a lower energy level and released

a specific amount of energy in the form of light

(photon).
 The energy of the photon is equal to the energy

difference between levels.

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Note :
Ground state is the lowest energy level an
electron will occupy in an atom at an ordinary
condition.

Excited state is a state /level where an electron

occupies after absorbing an amount of energy

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 HOW TO CALCULATE THE ENERGY
OF PHOTON?
 The energy emitted by an electron, E during
transition is calculated using:
 1 
E = Ef - Ei Where: Ei   RH  2 
 ni 
 1 
E f   R H  2 
 1    1   nf 
E  R H  2     R H  2  
  i – initial
 f  
n  i 
n f - final

Thus,
 1 1 
 E  RH  2  2 
n n  RH = 2.18 x 10-18 J
 i f  n = 1,2,3,………. ∞
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16
A photon of energy is emitted in the form of radiation with
appropriate frequency and wavelength.

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• Therefore, the energy change of an electron
during transition can be related as:

E  h
where : h (Planck's constant) = 6.63 x 10-34 J s
 = frequency (s-1)
• The wavelength and frequency can be related as:
c


where : c (speed of light) = 3.0 x 108 m s-1
Thus : hc
ΔE 
 18
 Electromagnetic Spectrum
• Electromagnetic spectrum is a series of rays that is
made up of the radiation in all kinds of wavelength.
• All electromagnetic waves travel through space
with the same speed. (which is the speed of light, c
= 3.0 x 108 m s-1)

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Regions of the Electromagnetic
Spectrum

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 Spectrum
• Spectrum can be defined as a series of
colours.
• Two types:
i. Continuous spectrum
ii. Line spectrum

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 Continuous Spectrum
 A spectrum consists of radiation distributed over
all wavelengths without any blank spot.
(no definite line that separate the colours)

Example : rainbow

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Formation of Continuous Spectrum

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 Line Spectrum
 A spectrum consists of discontinuous & discrete lines with
specific wavelength.
 It is composed when the light from a gas discharge tube
containing a particular element is passed through a prism.

 Example : hydrogen spectrum

• Two types line spectrum:

i) Emission spectrum
ii) Absorption spectrum

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 Continuous spectrum vs Line spectrum
Continuous Spectrum
• A spectrum consist of all
wavelength in a given range
without any line to separate the
colour.
• Formed when hot objects like
stars, moons emit
electromagnetic radiations at all
the wavelengths.
• Example: Rainbow
Line Spectrum
• A spectrum consist of few line
that represent a specific
wavelength.
• From when the light from a gas
discharge tube containing a
particular element is passed
through a prism.
• Example: Hydrogen spectrum
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Formation of Line Spectrum of Hydrogen Atom

Energy is supplied to the Hydrogen

gas in a discharged tube

Electrons of the hydrogen atoms absorb

energy and excite to a higher level

At the excited state, electrons are unstable

They fall to lower levels and produce

radiation (light) of a particular wavelength

Lights of a certain wavelength fall on the photograph

plate and lines are recorded
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 Hydrogen spectrum Series
• Ranges from the region of UV to IR

• Series are named after the scientist who

discovered them

• Classification done is based on which energy

level the electrons drop to

• Five main series:

– Lyman, Balmer, Paschen, Brackett and Pfund.

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 THREE SERIES OF SPECTRAL LINES OF
ATOMIC HYDROGEN
Balmer series
(Visible Region)

Lyman series Paschen, Bracket, Pfund series

(Ultraviolet Region) (Infrared Region)

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The series of Hydrogen Emission Spectrum
nf ni Name of Spectrum Region
series

1 2,3,4,… Lyman Ultraviolet (UV)

2 3,4,5,… Balmer Visible

3 4,5,6,… Paschen Infrared (IR)

4 5,6,7,… Brackett Infrared (IR)
5 6,7,8,… Pfund Infrared (IR)

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 Energy Level Diagram

The transition of
n=5 electrons to form
n=4
series of spectrum
Energy

n=3

n=2
The fall from any excited state to n=2
produces Balmer series

n=1

The fall from any excited state to n=1

produces a line in Lyman series
‫ג‬1 Balmer series

Line
Spectrum

First line in the Balmer series

(Electron falls from n=3 to n=2)

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 RELATIONSHIP BETWEEN ENERGY DIFFERENCE, ∆E,
WAVELENGTH, λ & FREQUENCY,ѵ

From the line spectrum below;

410.1 nm
656.3 nm 486.1 nm 434.1 nm

Wavelength, λ (nm)

λ, wavelength increase
ѵ, frequency decrease
E, energy decrease
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 Rydberg Equation
 Wavelength emitted by the transition of electron between
two energy levels is calculated using Rydberg equation:

1  1 1 
 RH  2  2  , n1 < n2
  n1 n2 
where:
RH (Rydberg constant) = 1.097  107 m-1
 = wavelength
n (principal quantum number) = 1,2,3,…. ∞)
Since  should have a positive value, thus n1 < n2

Note: wave number = 1


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 Ionisation Energy
Definition :
Ionisation energy is the minimum energy
required to remove one mole of electrons
from one mole of gaseous atom.
M(g) → M+(g) + e ∆H = +ve
• The electron of an atom has the lowest
energy at the ground state.

• At the ground state, there are strong attractive

forces between electrons and the nucleus.

• If the electron absorbs sufficient amount of energy,

it will promote to a higher energy level and
experience weaker nucleus attraction.

• When electron is no longer attracted by the

nucleus and is free from the nucleus attraction, the
electron is said to be ionised.

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  For hydrogen atom, the ionisation process
refer to the energy required to remove one
mole of electrons from n=1 to n= ∞.
 At n = ∞, the potential energy of electron is
zero, here the nucleus attractive force has no
effect on the electron (electron is free from
nucleus)
Bohr found that the closer an electron is to the
nucleus, the more energy it needs to ionize, but the
farther away it is, the less energy it needs to do so.
 The limitation of Bohr’s Theory
Bohr was successful in:
 Explaining the formation of line spectrum of

hydrogen atom and ions that containing only

one electron. Example: He+, Li2+
• However, Bohr’s theory unable to explain the
line spectrum of atom/ions containing more
than one electron.

3636
 de Broglie’s Postulate
 In 1924 Louis de Broglie proposed that not
only light but all matter has a dual nature and
possesses both wave and particle properties.
 de Broglie’s hypothesis is applicable to all
matter, any object, with mass, m and
velocity,v would have wave properties.
 Particle such as electron possesses dual
natures, which is both the wave and particle
properties.
De Broglie deduced that the particle and wave
properties are related by the expression:

h
λ=
mv
where:
λ = wavelength of particle
h = planck constant
m = mass of particle
v = velocity of particle
 Heisenberg’s Uncertainty Principle
It is impossible to know simultaneously both the momentum p
(defined as mass times velocity) and the position of a particle with
certain.
Stated mathematically,
h
xp 
4
Where:
Δx = uncertainty in measuring the position
Δp = uncertainty in measuring the momentum
Δp = Δmv
h = Planck constant
2.2 Quantum Mechanical Model
Learning Outcomes
At the end of this topic students should be able to:-
(a) define the term orbital.
(b) explain the four quantum numbers of an
electron in an orbital.
(c) sketch the 3-D shapes of s, p and d orbital.
 Introduction
• Quantum mechanics examines the wave motion
of objects on the atomic scale.

• Erwin Schrodinger derived an equation that is the

basic for the quantum mechanical model of the
hydrogen atom.

• The model describe an atom that has certain

allowed quantities of energy due to the allowed
wavelike motion of an electron whose exact
location is impossible to know.
• The position of an electron is described by a
probability distribution map called an orbital.

 An orbital is a three-dimensional region in

space around the nucleus where there is a high
probability of finding an electron.
 Quantum Numbers
Each of the electrons in an atom is described
and characterised by a set of four quantum
numbers:
 principal quantum number, n
 angular momentum quantum number, l
 magnetic quantum number, m
 electron spin quantum number, s.
 Principal Quantum Number, n
 n determines the energy level (electron shell)
and size of an orbital.
 The principal quantum number n, is an integer
n =1, 2, 3, …, ∞.
 As n increase :
i) the orbital become larger
ii) electron has higher energy
 n 1 2 3 4

Orbital size

Energy
increases
• The energy level, n is also called shell.

• The energy level n = 1 is the lowest energy level

with the smallest orbital size and nearest to the
nucleus.

• As the n increases, the energy and orbital size

increases and locate farther from the nucleus.
 Angular Momentum Quantum Number, l
 Alternative name:
- Subsidiary Quantum Number
- Azimuthal Quantum Number
- Orbital Quantum Number
 The value of l determines the shape of the orbital.
 The allowed values of l are 0, 1, 2,…, ( n - 1)
  Letters are assigned to different numerical values of l :

l Name of orbital Orbital shape

0 s spherical
1 p dumbbell
2 d cloverleaf
3 f
4 g
• A collection of orbitals with the same value of n
is called a shell.

• One or more orbitals with the same n and l

values are called sub-shell.
Shell, n Sub-shell, l Name of
sub-shell
n=1 l=0 1s

n=2 l=0 2s two subshells

l=1 2p (s and p-orbitals)
n=3 l=0 3s
l=1 3p three subshells
l=2 3d (s, p, and d
orbitals)
 Magnetic Quantum Number, m
 Describe the orientation of orbital in space.
 Possible values of m depend on the value of l.
For a given l, m can be : - l, …, 0, …, +l

 Example:
If l = 0, m = 0 (1 orientation of s orbital )
 If l = 1, m = -1, 0, +1

three p orbitals
(3 orientation of p orbitals: px, py, pz)

If l = 2, m = -2, -1, 0, +1, +2

five d orbitals
(5 orientation of d orbitals: dxy, dxz, dyz, dx-y, dy2)
2 2
 Electron Spin Quantum Number, s

 The value of s represent the direction of an

electron rotation on its own axis.
 either clockwise or anticlockwise

 It has 2 values : +½ and -½

 Shape of Atomic Orbital
(a) s orbitals
 The s orbital is represented by l = 0
 It has spherical shape with the nucleus at the
centre.
 The size of s orbital becomes larger as the value of
n increases.
The size of s orbital with different values of n.
(b) p orbitals

 The p orbitals are represented by l = 1

 They are dumb-bells and separated by a node at
the nucleus
 The l =1 , there are three possible values of m,
-1,0,+1, which refer to three p orbitals,
( px , py , pz )

 As n increases, the p orbitals get larger.

The shape and the orientation of p orbitals
(c) d orbitals

 The d orbitals are represented by l = 2

 All the d orbitals do not look alike.

 There are five possible m values: -2,-1, 0, +1, +2,
which correspond to five d orbitals with five different
orientations:
d xy , d yz , d xz , d x 2 -y2 , d z2
Shape of d orbital
 Description of electrons in
orbitals
The position of an electron in an orbital is given by the
set of four quantum numbers.

Example:
An electron that occupies the 2py orbital can be
described as having these quantum numbers:

n = 2, l = 1, m = -1 (or 0 or +1), s= +½ or -½
 Consider n = 1

Value of l; l = 0
Value of m ; m = 0

• Only one value of m shows one orientation only

• An electron in the 1s orbital may have the spin: +½ or -½
• The electron can be designated by these four quantum
numbers;
(n = 1,  =0, m = 0, s= +½) or (n= 1, =0, m=0, s=-½)

• Or simplified as ; (n, l , m , s) (n, l , m , s)

( 1,0, 0, +½ ) or (1, 0, 0, -½)
2.3 Electronic configuration

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 Learning Outcomes
At the end of this topic students should be able to:-
(a) Explain Aufbau principle, Hund's rule
and Pauli’s Exclusion Principle
(b) Predict the electronic configurations of atoms and
monoatomic ions using spdf notations.
(c) Justify the anomalous electronic configurations
of copper and chromium.
 Introduction
 Electronic configuration of an atom describes the
arrangement of electron in an atom.
• Electron arrangement in an atom can be represented
by:
i. Electronic configuration/notation:
Example : 1H : 1s1 Shows total number of electron
Represents energy
level or the orbital

ii. Orbital diagram:

Example :1H : Represents electrons with the
1s energy level of 1s and spin of +½
These rules are applied to describe how the
electrons are filled into atomic orbitals of an atom:

i. Aufbau Principle
ii. Pauli Exclusion Principle.
iii. Hund’s Rule
 Aufbau Principle
 Aufbau principle states that electrons are filled
in atomic orbitals in the order of increasing
energy.
 Electrons should occupy the orbital with the
lowest energy first before enters the one with
higher energy.
Order of increasing energy level:
1s < 2s < 2p < 3s< 3p < 4s< 3d < 4p < 5s…
Tips to remember the order:
 Hund’s Rule
 Hund’s rule states that when electrons are filled
into the orbital of equivalent energy (degenerate
orbitals), each orbital is filled singly with electron
of the same spin before it is paired.
 Degenerate orbitals are the orbitals with
equivalent or identical energy.
 Example : the three p orbitals (px , py , pz )
and five d orbitals ( dxy , dyz , dxz , d 2 2 , d 2 )
x y z
Example:
Nitrogen atom, 7N
Z = 7 (7 electrons)

7N :
1s 2s 2p

Electronic configuration of N atom:

 Pauli’s Exclusion Principle
 Pauli’s exclusion principle states that no two
electrons in an atom can have the same set of
four quantum numbers (n, l, m, s).
Example:
Consider the electronic configuration of Helium:
2He: 1s 2 or
1s
Has the quantum number of: Has the quantum number of:
n=1, l=0, m=0, s=+1/2 n=1, l=0, m=0, s= -1/2
or or
(n,l,m,s) = (1,0,0,+1/2) (n,l,m,s) = (1,0,0,-1/2)
Electronic Configurations Of Ions

• Ions are formed when atoms gain or lose

electrons.
• To form positive ions (cations), electrons are
removed from the outermost orbital
• To form negative ions (anions), electrons are
added to the outermost orbitals