CHAPTER 2

ATOMIC STRUCTURE
2.1 Bohr’s Atomic Model
 Learning Outcomes

At the end of this topic students should be able

to:-
a) Describe the Bohr’s atomic model.
b) Explain the existence of electron energy
levels in an atom.
c) Calculate the 1
energy of electron at its
−18 level
E n =− R H 2 , R H =2.18x10 J
(orbit) using. n
 Learning Outcomes

d) Describe the formation of line spectrum of

hydrogen atom.
e) Calculate the energy change of an electron
1 1
 E=
during RH

transition.
2
− 2
n1 n2  where R H = 2.18×10
−18
J

f) Calculate the photon of energy

 E =h  where  =c /
emitted by an
electron that produces a particular
wavelength during transition.
 Learning Outcomes
g) Perform calculation involving the Rydberg
equation for Lyman, Balmer, Paschen,
1 1 1
Brackett

= R

H and
2
−
n1 n2 
Pfund
2 series:
where R H =1.097×10
7
m
−1

n1 n2

g) Calculate the ionisation energy of hydrogen

atom from the Lyman series.
 Learning Outcomes

i) State the weaknesses of Bohr’s atomic

model.
j) State the dual nature of electron using de
Broglie’s postulate and Heisenberg’s
uncertainty principle.
Bohr’s Atomic Model
 In 1913, a young
Dutch physicist, Niels
Böhr proposed a
theory of atom that
shook the scientific
world.

The atomic model he
described had
electrons circling a
central nucleus that
contains positively
change proton.
 Bohr’s Atomic Model
 Böhr also proposed
that these orbits can
only occur at
specifically
“permitted” levels
according to the
energy levels of the
electron and explain
successfully the lines
in the hydrogen
spectrum.
 Bohr’s Atomic Model
First Postulates
 Electron moves in
circular orbits about
the nucleus.
 While moving in the
orbit, the electron
does not radiate or
absorb any energy.
 [orbit = energy level=shell]

 Orbit is a pathway where the electron is move

around the nucleus.

Orbit
 Bohr’s Atomic Model
Second Postulate
 The moving electron
has a specific amount
of energy; its energy
is quantised.
The energy of an electron in its level is given by:

1
E n =−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
Bohr’s Atomic Model
Third postulate
 At ordinary conditions,
the electron is at the
ground state (lowest
level).
 If energy is supplied,
electron absorbed the
energy and is promoted
from a lower energy
level to a higher ones.
(Electron is excited)
 Bohr’s Atomic Model
Fourth Postulate
 Electron at its excited states is unstable.
 It will fall back to lower energy level and
released a specific amount of energy in the
form of light (photon).
 The energy of the photon equals the energy
difference between levels.
 E le c tr o n is e x c it e d fr o m lo w e r t o h ig h e r
e n e r g y le v e l.
A s p e c ific a m o u n t o f e n e r g y is a b s o r b e d
E = h  = E 3-E 1

n =1 n = 2 n = 3 n = 4

E le c tr o n f a lls fr o m h ig h e r t o lo w e r e n e r g y le v e l .
A p h o to n is e m itt e d .
 E = h  = E 1-E 3
 Radiant energy emitted when the electron
moves from higher-energy state to lower-
energy state is given by:

 E = Ef − E i
Where:

1
E f =−R H
 1
2
nf
E i=−R H
 
2
ni

 1    1   1 1 
E  R H  2     R H  2   Thus, E  R H  2  2 
n 
n  n   i n f 
 f    i 
 The amount of energy released by the
electron is called a photon of energy.

A photon of energy is emitted in the form of
radiation with appropriate frequency and
wavelength.
  E = hv

Where : h (Planck's constant) = 6.63 x 10-34 J s

v = frequency (s-1)
c
=
v
Where : c (speed of light) = 3.00 x 108 ms-1
hc
Thus : ΔE 

 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  7
where R H =1.097×10 m
−1

n1 n2
 Example 1
 Calculate the wavelength, in nanometers of the
spectrum of hydrogen corresponding to n = 2
and n = 4 in the Rydberg equation.
 Exercises:
1. Calculate the energy of hydrogen electron in the:

(a) 1st orbit

(b) 3rd orbit

(c) 8th orbit

1. Calculate the energy change (J), that occurs when an

electron falls from n = 5 to n = 3 energy level in a
hydrogen atom.

2. Calculate the frequency and wavelength (nm) of the

radiation emitted in question 2.
 Emission Spectra
Emission Spectra

Continuous Line
Spectra Spectra
 Continuous Spectrum
 A spectrum consists of radiation distributed
over all wavelength without any blank spot.
 Example : electromagnetic spectrum, rainbow
 It is produced by white light (sunlight or
incandescent lamp) that passed through a
prism
Formation of Continuous Spectrum
Regions of the Electromagnetic Spectrum
 Line Spectrum (atomic 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.
 Formation of Atomic / Line
Spectrum
 The emitted light (photons) is then separated
into its components by a prism.

Each component is focused at a definite
position, according to its wavelength and forms
as an image on the photographic plate.

The images are called spectral lines.
Formation of Atomic / Line
Spectrum
 Formation of Atomic / Line
Spectrum
 Example : The line emission spectrum of
hydrogen atom
 Line spectrum are composed a few
wavelengths giving a series of discrete line
separated by blank areas
 It means each line corresponds to a specific
wavelength or frequency.
 Formation of Line Spectrum
 When electron absorbed radiant energy, they
will move from lower energy level to higher
energy level (excited state).
 This excited electron is unstable and it will fall
back to lower energy level.
 During the transition, electron will release
energy in the form of light with specific
wavelength and can detected as a line
spectrum.
 Differences Between Line &
Continuous Spectra
Continuous Spectrum Line Spectrum
 A spectrum that  A spectrum that
contains all contain only specific
wavelength without wavelengths.
any blank spots.  A spectrum of
 Example: Rainbow. discrete lines with
certain wavelengths.
 Example: Emission
spectrum an element.
 Formation of Line Spectrum
(Lyman Series)
n=∞
n=5
n=4

Energy n=
3
n=2

n=
1 Emission of photon
Line E
spectrum λ
Lyman Series
 Formation of Line Spectrum
(Balmer Series)
n=∞
n=5
n=4

Energy n=3

n=2

n=1
Emission of photon
Line E
spectrum λ
Lyman Series Balmer Series
Energy Level in Hydrogen Atom
 Example
Complete the following table
Spectrum
Series nf ni
region

Lyman 1 2,3,4,… ultraviolet

Balmer 2 3,4,5,… Visible/uv

Paschen 3 4,5,6,… Infrared

Brackett 4 5,6,7,… Infrared

Pfund 5 6,7,8,… Infrared

 Example
 The following diagram is the line spectrum of
hydrogen atom. Line A is the first line of the
Lyman series.
A B C D E E
Line λ
spectrum v

Specify the increasing order of the radiant energy,

frequency and wavelength of the emitted photon.
Which of the line that corresponds to
i) the shortest wavelength?
ii) the lowest frequency?
 Example
The line spectrum of Balmer is given as below:
W Y

Describe the transitions of electrons that lead to the lines

W, and Y, respectively.
Solution

For W: transition of electron is from n =4 to n = 2

For Y: electron shifts from n = 7 to n = 2
 Example
E D C B A
Line
spectrum Paschen series

(a) Which of the line in the Paschen series

corresponds to the longest wavelength of
photon?

(b) Describe the transition that gives rise to the line.

Solution
Line A.
The electron moves from n=4 to n=3.
 Example
With refer to the second line in the Balmer series of the
hydrogen spectrum, Calculate;

a)the wavelength in nm

b)the frequency

c)the energy
 Example
Refer to last line of hydrogen spectrum in Lyman
series, Calculate:

a) Wavelength

b) Frequency

c) Wave number; where wave number = 1


For Lyman series; n1 = 1 & n2 = ∞
Ans:
i. 9.116 x10-8 m
ii. 3.29 x1015 s-1
iii. 1.0970 X 107 m-1
 Ionization Energy
Defination : Ionization energy is the minimum
energy required to remove an electron in its
ground state from an atom (or an ion) in
gaseous state.

M (g) → M+ (g) + e ∆H = +ve

 Ionization Energy
 The hydrogen atom is ionised when electron is
removed from its ground state (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)
 Example
n1 = 1, n2 = ∞
∆E = RH (1/n12 – 1/n22)
= 2.18 x 10-18 (1/12 – 1/∞2)
= 2.18 x 10-18 (1 – 0)
= 2.18 x 10-18 J
Ionisation energy
= 2.18 x 10-18 x 6.02 x 1023 J mol-1
= 1.312 x 106 J mol-1
= 1312 kJ mol-1
 Example
Calculate the energy to ionized :
(a) a hydrogen atom.
(b) 1 mol of hydrogen atom.
Solution
(a)
1 1
 E=− R H
 2
− 2
n1 n2 
1 1
=−2.18×10 −18
 1 2
− 2
∞ 
−18
=2.18×10 J
Solution
(b) 1 H atoms need 2.18 x 1018 J

1 mol H atom

= 2.18 x 1018 x 6.02 x 1023

= 1.31 x 106 J

The energy to ionized 1 mol of hydrogen atom is

1.31 X 106 J
 Example
10.97 10.66 10.52 10.27 9.74 8.22

The Lyman series of the spectrum of hydrogen is

shown above. Calculate the ionisation energy of
hydrogen from the spectrum.
Solution
ΔE = h X c/λ = h x c x wave no.
= (6.626x10-34 Js)(3x108 ms-1)(10.97x106 m-1)
= 218.06 x 10-20 J
= 2.18 x 10-18J

Ionisation energy
= (2.18 x 10-18) (6.02x1023 J mol-1)
= 1.312 x 106 J mol-1
= 1312 kJ mol-1
 The weaknesses of Bohr’s Theory
 It can only explain the hydrogen spectrum or
any spectrum of ions contain one electron.
example: He+, Li2+.Therefore, it did not account
for the emission spectrum of atom containing
more than 1 electron.

Electron are wavelike, we can’t define the
precise location of a wave because a wave
extends in space.
 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.

Electron is both particle and wave.

Tiny particle such as electron does have wave
properties.

De Broglie deduced that the particle and wave
properties are related by the expression:
 Example
Electron has dual nature properties. Why don't
we see the wave properties of a Baseball?
 de Broglie’s Postulate

h
=
mμ
h = Planck constant (J s)
m = particle mass (kg)
μ = velocity (m/s)
λ = wavelength of a matter wave
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≥
4π
where Δx = uncertainty in measuring the position
Δp = uncertainty in measuring the momentum
= Δmv
h = Planck constant
2.2 Quantum Mechanical Model
 Learning Outcomes
At the end of this topic students should be able
to:-
 Define the term orbital.
 State the four quantum numbers in an orbitals.
 sketch the 3-D shape of s, p and d orbitals.
 Atomic Orbital
Definition

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, namely

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, may have +ve
value starting from n =1, 2, 3, …, ∞.

As n increase :

i) the orbital become larger

ii) electron has higher energy

 Principal Quantum Number, n

n 1 2 3 4

Orbital size

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

Value of l Symbol Orbital shape

0 s spherical
1 p dumbbell
2 d cloverleaf
3 f
 Angular Momentum Quantum
Number, l
 value is depend on n. (i.e., 0 ≤ l < n).
If n = 1, l = 0 (s-orbital) One subshell
(s orbital)
If n = 2, l = 0 (s-orbital)
two subshells
= 1 (p-orbital) (s and p orbitals)

If n = 3, l = 0 (s-orbital)
three subshells
= 1 (p-orbital) (s, p, and dorbitals)
= 2 (d-orbital)
 Magnetic Quantum Number, m
 Describe the orientation of orbitals 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 » 3 orientation of p orbital
(px, py, pz)
If l = 2, m = -2,-1, 0,+1,+2 » 5 orientation of d orbital

( dxy,dxz,dyz,dx2-y2,dz2)
 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 value : +½ and -½
 Shape of Atomic Orbital
s orbitals

Spherical shape with the nucleus at the centre.

When l = 0 , m = 0 , only 1 orientation of s
orbital.

The larger value of n, the size of s orbital gets
larger.
Shape of s orbital with different n

Z Z Z

Y Y Y

X X X

1s 2s 3s
 Shape of Atomic Orbitals
p orbitals

Can be represent as a pair of dumb-bell shaped

When l = 1, m = -1, 0, +1

 3 orientation of p-orbitals px, py, and pz.


As n increases, the p orbitals get larger.
 Shape of p orbital

px
py pz
 Shape of Atomic Orbitals
d orbitals

All the d orbitals do not look alike.


When l = 2 , m = -2, -1, 0, +1, +2.


There are five orientation of d orbitals.
 Shape of d orbital

dx2-y2 dz2 dxy

dxz dyz
 Set of Four Quantum Numbers
 4 quantum number n,l,m and s enable us to
label completely an electron in any orbital of an
atom. Example:

4 quantum numbers of 2s orbital electron are

n = 2 , l = 0 , m = 0 and s = +½ and -½

Can be simplified as (2,0,0,+½)
n, l , m, s or (2,0,0,-½)
n, l , m, s
 Exercise

Orbital
Shell n l m No. of orbitals
notation

1 1 0 1s 0 1
0 2s 0 1
2 2
1 2p -1,0,+1 3
 Exercise
 Predict the following quantum numbers whether
they are allowed or not

(a) (1,0,0,-½)

(b) (2,0,1,1)

(c) (0,1,1,+½)

(d) (4,1,0,-½)
2.3 Electronic Configuration
 Learning Outcomes
At the end of this topic students should be able to:-

State and apply Aufbau principle, Hund's rule and
Pauli exclusion principle in filling of electrons in
orbitals of an atom.

Write the electronic configuration of atoms and
monoatomic ions.

(a) Orbital diagram

(b) spdf notation

 Learning Outcomes
 Explain the anomalous electronic configurations
of chromium and copper.
 Introduction
 The electronic configuration of an atom show
how electron are filled in the orbital.

Electronic configuration describes the
arrangement of electron in an atom.
 Electronic Configuration
Method 1: Orbital diagram
Example: 8O

Box

1s 2s 2p
 Electronic Configuration
Method 2: s,p,d,f notation
Number of electrons
Example: 8O in the subshells

1s 2s 2p
2 2 4

Principal quantum Azimuthal quantum

number, n number, l
 Electronic Configuration
To enable us to do electronic configuration, we
have to obey the following rules:

a) The Aufbau Principle

b) The Pauli Exclusion Principle

c) The Hund rule

 Aufbau Principle
 State that electrons are filled in the orbitals in
order of increasing energy.

Electrons should occupy the orbital with the
lowest energy first before enters the one with
higher energy.
 Relative Energy Level
of Atomic Orbitals
4d
n=5 5s

4p

n=4 3d
4s
energy
Energy

n=3 3p
3s Orbital energy levels
in a many-electron atom
n=2 2p
2s

n=1
1s
Order of orbitals (filling) in multi-electron atom
Order of orbitals (filling) in multi-electron atom


The order of filling orbitals is:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s

Start with the 1s orbital and move downward,
following the arrows. Example:
(a) 4Be (b) Ne
10

Electronic configuration 4Be : 1s2 2s2

Electronic configuration 10Ne : 1s2 2s2 2p6

 Pauli Exclusion Principle
 No two electrons in an atom can have the same
four quantum numbers (n, l, m, s).

Eg : Li (3 electrons)
 Hund’s Rule
 States that when electrons are added to the
orbital of equivalent energy (degenerate
orbitals), each orbital are filled singly with
electron of the same spin first before it is
paired.

The electron in half-filled orbitals have the same
spins, that is, parallel spins.
 Example
1) Carbon (6 electron)

1s 2s 2p
2) Oxygen (8 electron)

1s 2s 2p
 Exercise
Write the electronic configuration of the following
atom or ion:
(a)C
(b)Ne
(c)Al
(d)Al3+
(e)Cl
(f) Cl-
 The Anomalous Electronic
Configurations of Cr and Cu
Cr and Cu have electron configurations which are
inconsistent with the Aufbau principle. The
anomalous are explained on the basis that a
filled or half-filled orbital is more stable.

Expected (Aufbau
Element Observed/actual
Principle)

Cr (Z=24) 1s22s22p63s23p6 4s2 3d4 1s22s22p63s23p6 4s1 3d5

Cu (Z=29) 1s22s22p63s23p6 3d9 4s2 1s22s22p63s23p6 3d10 4s1

 Orbital diagram

 Cr :
24 [Ar]
18
3d 4s

3d orbital with a half filled orbital arrangement are more

stable.

Actual
24Cr : 18[Ar]

3d 4s

18
Ar : 1s 2
2s 2
2p 6
3s 2
3p6

*Half filled orbital arrangement increase stability of Cr atom

Copper expected orbital notation (Aufbau Principle)

 Cu : 18
[Ar]
3d 4s

3d orbital with fully filled orbital arrangement is more stable.

Copper actual orbital notation

 Cu : 18
[Ar]
3d 4s

18
Ar : 1s 2
2s 2
2p 6
3s 2
3p6