CHAPTER 2

ATOMIC STRUCTURE
2.1 Bohr’s Atomic Model

2.2 Quantum Mechanical Model

2.3 Electronic Configuration

1
 LECTURE 1

2.1 Bohr’s Atomic

Model

2
1
n2

Bohr’s Atomic Model

At the end of this topic students should be able to:-

a) Describe the Bohr’s atomic models.

b) Explain the existence of electron energy levels in an
atom.
c) Calculate the energy of electron using :
En = - RH (1/n2) ,
RH = 2.18 x 10-18 J

3
BOHR’S ATOMIC MODELS

In 1913, a young Dutch physicist,

Niels Bohr proposed a theory of
atom that shook the scientific world.
The atomic model he described
had electrons circling a central
nucleus that contains positively
charged protons.
Bohr also proposed that these orbits can only
occur at specifically “permitted” levels only
according to the energy levels of the electron
and explain successfully the lines in the 4
hydrogen spectrum.
 BOHR’S ATOMIC POSTULATES

1. Electron moves in circular orbits about the nucleus. In

moving in the orbit, the electron does not radiate any
energy and does not absorb any energy.

H
Nucleus 1
(proton) 1H

5
 BOHR’S ATOMIC POSTULATES

2. The energy of an electron in a hydrogen atom is

quantised, that is, the electron has only a fixed set of
allowed orbits, called stationary states.
[ orbit = stationary state = energy level = shell ]

n=1
H Nucleus
(proton)
n=3

n=2 6
 BOHR’S ATOMIC POSTULATES

3. 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)

4. 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. The energy of the photon
equals the energy difference between levels.

7
 BOHR’S ATOMIC MODELS

1. Electron moves in circular orbits about the nucleus. In

moving in the orbit, the electron does not radiate any
energy and does not absorb any energy.

2. The energy of an electron in a hydrogen atom is

quantised, that is, the electron has only a fixed set of
allowed orbits, called stationary states.
[ orbit = stationary state = energy level = shell ]

8
 Energy levels in an atom

 Ground state
the state in which the electrons have their lowest energy

 Excited state
the state in which the electrons have shifted from a lower
energy level to a higher energy level

 Energy level
energy associated with a specific orbit or state

9
 THE ENERGY LEVEL
 The energy of an electron in its level is given by:

 1 
E n  R H  2 
n 
RH (Rydberg constant) or A = 2.18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
 Energy associated with forces of attraction are taken to be
negative (thus, negative sign)
10
 LECTURE 2
At the end of this topic students should be able to:-

d) Describe the formation of line spectrum of hydrogen

atom
e) Calculate the energy change of an electron during
transition.
E = RH (1/n12 - 1/n22) ,
where RH = 2.18 x 10-18 J
f) Calculate the photon of energy emitted by an electron
that produces a particular wavelength during transition
E = h where = c/λ
11
 Emission Spectra

Emission Spectra

Continuous Line
Spectra Spectra

12
 Continuous Spectrum
A spectrum consists all wavelength components
(containing an unbroken sequence of frequencies) of the
visible portion of the electromagnetic spectrum are
present.
It is produced by incandescent solids, liquids, and
compressed gases.

13
Regions of the Electromagnetic Spectrum

14
FORMATION OF CONTINUOUS SPECTRUM

 When white light from

incandescent lamp is passed
through a slit then a prism, it
separates into a spectrum.

 The white light spread out into

a rainbow of colours produces
a continuous spectrum.

 The spectrum is continuous in

that all wavelengths are
presents and each colour
merges into the next without a
break.
15
Line Spectrum (atomic spectrum)
A spectrum consists of discontinuous & discrete lines produced by
excited atoms and ions as the electrons fall back to a lower energy
level. The radiation emitted is only at a specific wavelength or
frequency. It means each line corresponds to a specific wavelength
or frequency.
Line spectrum are composed of only a few wavelengths giving a
series of discrete line separated by blank areas

16
FORMATION OF ATOMIC / LINE SPECTRUM

film
prism

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.
17
FORMATION OF ATOMIC / LINE SPECTRUM

n= Radiant energy (a

n=5 quantum of energy)
n=4
Energy

absorbed by the atom (or

n=3 electron) causes the
electron to move from a
n=2
lower-energy state to a
higher-energy state.
Hydrogen atom is said to
be at excited state (very
unstable).
n=1

When an electrical discharge is passed through a sample of

hydrogen gas at low pressure, hydrogen molecules decompose to
form hydrogen atoms. 18
 FORMATION OF ATOMIC / LINE SPECTRUM

n=
n=6 When the electrons fall
n=5
Energy

back to lower energy

n=4 levels, radiant energies
(photons) are emitted in
the form of light
n=3
(electromagnetic radiation
of a particular frequency or
wavelength)

n=2

Emission of photon
19
FORMATION OF ATOMIC / LINE SPECTRUM
n=
n=5
n=4

Energy n=3

n=2

n=1
Emission of photon
Line E
spectrum 
Lyman Series 20
FORMATION OF ATOMIC / LINE SPECTRUM
n=
n=5
n=4

Energy n=3

n=2

n=1
Emission of photon
Line E
spectrum 
Lyman Series Balmer Series 21
 Emission series of hydrogen atom

n=
Pfund series
A
n=4 E4   2
4
Brackett series A
n=3 E3   2
3
Paschen series A
n=2 E2   2
2
Balmer series

Lyman series A
n=1 E1  
12
22
Exercise: Complete the following table

Spectrum
Series n1 n2
region

Lyman 2,3,4,…

2 3,4,5,…
Paschen 4,5,6,… Infrared

4 5,6,7,… Infrared

5 6,7,8,… Infrared 23
 Exercise
The following diagram depicts the line spectrum of
hydrogen atom. Line A is the first line of the Lyman
series.
A B C D E
Line E
spectrum 

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? 24
 Exercise
W Y
Line
spectrum Balmer series

Describe the transitions of electrons that lead to

the lines W, and Y, respectively.

Solution

25
Homework
Calculate En for n = 1, 2, 3, and 4. Make a one-
dimensional graph showing energy, at different
values of n, increasing vertically. On this graph,
indicate by vertical arrows transitions that lead to
lines in
a) Lyman series
b) Paschen series

26
 Significance of Atomic Spectra
 In Lyman series, the frequency of the convergence of
spectral lines can be used to find the ionisation energy of
hydrogen atom:
IE = h
 The frequency of the first line of the Lyman series > the
frequency of the first line of the Balmer series.


Line E
spectrum 
Balmer Series Lyman Series 27
 Exercise
E D C B A
Line
spectrum Paschen series

Which of the line in the Paschen series corresponds to the

longest wavelength of photon?
Describe the transition that gives rise to the line.

Solution

28
 Energy calculation
 Radiant energy emitted when the electron moves from
higher-energy state to lower-energy state is given by the
difference in energy between energy levels:
where
E = Ef - Ei  1 
E i  R H  2 
 ni 
 1    1 
E  R H  2     R H  2  
   1 
 f  
n  i 
n
E f  R H  2 
 nf 
Thus,  1 1 
E  R H  2  2 
 ni nf 
29
 Energy calculation
 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.

where;
E = h h (Planck’s constant) =6.63  10-34 J s
 = frequency

Where; c
 c (speed of light) = 3.00108 ms-1

Thus, hc
ΔE 
 30
 Electron is excited from lower to higher
energy level. A specific amount of energy
is absorbed
E = h = E1-E3 (+ve)

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

Electron falls from higher to lower energy level .

A photon of energy is released.
E = h = E3-E1 (-ve)
31
 Energy level diagram for the hydrogen atom
n=

n=4
Potential energy

n=3

n=2

Energy Energy
absorbed released
n=1
32
 Exercises:
1) Calculate the energy of an electron in the second
energy level of a hydrogen atom. (-5.448 x 10-19 J)

2) Calculate the energy of an electron in the energy level

n = 6 of an hydrogen atom.

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

electron falls from n = 5 to n = 3 energy level in a
hydrogen atom.
(answer: 1.55 x 10-19J)

4) Calculate the frequency and wavelength (nm) of the

radiation emitted in question 3.
33
 LECTURE 3
At the end of this topic students should be able to:-

g) Perform calculations involving the Rydberg equation for Lyman,

Balmer, Paschen, Brackett and Pfund series .
1/ λ = RH (1/n12 - 1/n22) ,
where RH = 1.097 x 107 m-1 and n1<n2

h) Calculate the ionisation energy of hydrogen atom from

Lyman series.

i) State the weaknesses of Bohr’s atomic model.

j) State the dual nature of electron using the Broglie’s postulate

and Hesseinberg’s uncertainty principle.
34
 Rydberg Equation
 Wavelength emitted by the transition of electron
between two energy levels is calculated using
Rydberg equation:

1  1 1 
 R H  2  2
λ  n1 n2 
where
RH = 1.097  107 m-1
 = wavelength
Since  should have a positive value thus n1 < n2

35
 Example

Calculate the wavelength, in nanometers of the spectrum

of hydrogen corresponding to ni = 2 and nf = 4 in the
Rydberg equation.

Solution:
Rydberg equation:
1/λ = RH (1/22 – 1/42)
= RH(1/4-1/16)
1/λ = RH (1/ni2 – 1/nf2)
λ = 4.86m x 102 m
ni = 2 nf = 4
= 486nm
RH = 1.097 x 10m7

36
 Example
Use the Rydberg equation to calculate the wavelength of the
spectral line of hydrogen atom that would result when an
electron drops from the fourth orbit to the second orbit, then
identified the series the line would be found.

Solution:

1/λ = RH (1/n1 2 – 1/n2 2)

n1 = 2 n2 = 4

1/λ = 1.097 x 107 (1/22 – 1/42)

λ = 4.86 x 10-7 m
= 486 nm
*e dropped to the second orbit (n=2),
>>> Balmer series 37
EXAMPLE 3

Calculate the wavelengths of the fourth line in the

Balmer series of hydrogen.

n1 = 2 n2 = 6
RH = 1.097 x 107m-1

1 1 1
= RH
λ 22 62

λ = 4.10 x 10-7 m

38
 Different values of RH and its usage

1. RH = 1.097  107 m-1

1 1 1
= RH
λ n12 n22
n1 < n2

RH = 2.18 x 10-18 J
 1 1 
E  R H  2  2 

 ni nf  39
 EXAMPLE 4
Calculate the energy liberated when an electron
from the fifth energy level falls to the second
energy level in the hydrogen atom.

1 1 1
= RH hc
λ n2 n2 ΔE 
1 2

1 1 1 ΔE = (6.63  10-34Js)X(3.00108 ms-1)
=1.097 x 107 X (0.2303 X 107 m-1)
λ 22 52

1
= 0.2303 X 107 m-1 ΔE = 4.58 x 10-19 J
λ
40
 EXERCISE
Calculate what is;
i ) Wavelength
ii ) Frequency
iii ) Wave number of the last line of hydrogen spectrum
in Lyman series
Wave number = 1/wavelength

For Lyman series; n1 = 1

& n2 = ∞
Ans:
i. 9.116 x10-8m
ii. 3.29 x1015 s-1
iii. 1.0970 X 107 m-1
41
 Ionization Energy

 Definition : Ionization energy is the minimum energy

required to remove one mole of electron from one mole
of gaseous atom/ion.
M (g)  M+ (g) + e H = +ve

 The hydrogen atom is said to be 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).
42
 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 -18x 6.02 X 1023J mol-1
=1.312 x 106 J mol-1
= 1312 kJ mol-1
43
 Finding ionisation energy experimentally:

Convergent limit 1 st line

 1

Ionisation energy is determined by detecting

the wavelength of the convergence point

44
Example

10.97 10.66 10.52 10.27 9.74 8.22

wave number (x106 m-1)

The Lyman series of the spectrum of hydrogen is shown

above. Calculate the ionisation energy of hydrogen from
the spectrum.

45
 Solution
ΔE = hc/λ
=h x c / λ = h x c x wave no.
= 6.626 x 10-34 J s x 3 x 108 m s-1 x 10.97x 106 m-1
= 218.06x 10-20 J
= 2.18 x 10-18J

Ionisation energy
= 2.18 X 10 -18x 6.02 X 1023 J mol-1
=1.312 x 106 J mol-1
= 1312 kJ mol-1
46
 Exercise

Compute the ionisation energy of hydrogen atom

in kJ mol1.

Solution

J
47
 The weakness of Bohr’s Theory

1. His theory could not be extended to predict the energy

levels and spectra of atoms and ions with more than
one electron. It only can explain the hydrogen spectrum
or ions contain one electron eg He+, Li2+.

2. Electrons are restricted to orbit the nucleus at certain

fixed distances

3. It cannot explain for the dual nature of electron

4. It cannot explain for the extra lines formed in the

hydrogen spectrum. 48
 Point to Ponder

Davisson & Germer observed the diffraction of

electrons when a beam of electrons was directed at a
nickel crystal. Diffraction patterns produced by
scattering electrons from crystals are very similar to
those produced by scattering X-rays from crystals. This
experiment demonstrated that electrons do indeed
possess wavelike properties.
Thus, can the ‘position’ of a wave be specified???

49
 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
corpuscular properties. De Broglie deduced that the particle
and wave properties are related by the expression:

h
 = m

h = Planck constant (J s)
m = particle mass (kg)
 = velocity (m/s)
 = wavelength of a matter wave 50
 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 x = uncertainty in measuring the position

p = uncertainty in measuring the momentum
= mv
h = Planck constant
51
 LECTURE 4

2.2 QUANTUM
MECHANICAL MODEL

52
1
n2

At the end of this topic students should be able

to:-
a) Define the term orbital.
b) State the four quantum numbers of an
electron in an orbital (n, ,m,s).
i) principal quantum number, n
ii) angular momentum quantum number, 
iii) magnetic quantum number, m
iv) electron spin quantum number, s.
53
 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.

54
 Quantum Numbers

Each of the electrons in an atom is described and

characterised by a set of four quantum numbers, namely
a) principal quantum number, n
b) angular momentum quantum number, 
c) magnetic quantum number, m
d) electron spin quantum number, s.

55
 Principal Quantum Number, n

 The value of n determines the energy of an orbital and thereby

the energy of the electron in that particular orbital.

 The principal quantum number may have only integral values: n

=1, 2, 3, …, .

n 1 2 3 4

shell K L M N

Orbital size

Energy
increases 56
 Angular Momentum Quantum Number, 
- Alternative name: Subsidiary / Azimuthal / Orbital
Quantum Number

- The value of  indicates the shape of the atomic orbital (AO), the
types of orbitals, and the angular momentum of the electron.
- The allowed values of  are 0, 1, 2,…, (n1)

Letters are assigned to different numerical values of .

Numerical value of  Symbol Orbital shape
0 s spherical
1 p dumbbell
2 d cloverleaf
57
3 f
 Angular Momentum Quantum Number, 

-  is dependant on n. (i.e., 0   < n).

If n = 1,  can only be 0 (s-orbital)

If n = 2,  can be 0 or 1 giving rise to two subshells
(s and p-orbitals) of slightly different energy.
If n = 3,  can be 0, 1, or 2 (there are three subshells:
(s, p, and d-orbitals)

58
 Magnetic Quantum Number, m

 The direction or orientation of the magnetic field is determined

by the value of m.
 Possible values of m depend on the value of . For a given , m
can be : , …, 0, …, +
(  m  +)
If  = 0, m can only be 0  one orbital in s-subshell
If  = 1, m can be 1, 0, +1  three orbitals in p-subshell
If  = 2, m can be 2, 1, 0, +1, +2  five orbitals in d-subshell

59
 Magnetic Quantum Number, m

The number of m values indicates the number of orbitals in

a subshell with a particular  value.

The values of n = 2 and  = 1 indicate that we have a 2p-

subshell, and in this subshell we have three 2p-orbitals
(because there are three values of m, given by -1, 0 and
+1)

60
 Electron Spin Quantum Number, s
 The value of s determines the direction of spinning motions of an
electron (either clockwise or counter clockwise) which is spinning
on its own axes, as Earth does.
 The electron spin quantum number has a value of

1 1
+ or -
2 2

61
 Points to Remember

Atomic orbitals with the same energy (i.e., the same value
of n and ) are said to be degenerated. Therefore, there are
(2+1) degenerate orbitals for each value of .

The maximum number of electrons in a particular energy

level, n is given by the expression as follows:
max no. of e = 2n2

62
 Exercise: Complete the following table

 m No. of
Orbital
Shell n degenerated
(<n) notation (-  m  +)
orbitals
K 1

L 2

M 3

63
 Exercise
State whether or not each of the following symbols is an
acceptable designation for an atomic orbital. Explain what
is wrong with the unacceptable symbols.

a) 2d

b) 6g

c) 7s

d) 5i
64
 LECTURE 5
At the end of this topic students should be able to:-

c) Sketch the shapes of s,p and d orbitals

with the correct orientations.

65
 Shape of Atomic Orbitals
a) s orbitals
 Spherical shape with the nucleus at the centre.
 The probability of finding electrons at the
distance r from the nucleus is the same from all
direction.
 When l = 0
 As n increases s orbital
 gets larger

Shape of s orbital 66

with different n
 Shape of Atomic Orbitals
b) p orbitals
 When l = 1
 dumbbell shaped
 three p-orbitals px, py, and pz.
 correspond m of -1, 0, and +1.
 As n increases, the p-orbitals get larger.
 All p-orbitals have a node at the nucleus.

67
 Shape of Atomic Orbitals

 shape; four d orbitals have four lobes (perpendicular),

one d orbital has two major lobes along z axis
and a donut-shaped girdles the centre.

 When l = 2
m = -2, -1,0,1,2

 the orbitals are: dyz, dxz, dxy, dx2-y2, dz2

68
69
Shape of Atomic Orbitals

70
 LECTURE 6 & 7

2.3 ELECTRONIC CONFIGURATION

71
1
n2

Electronic Configuration
At the end of this topic students should
be able to:-
a) State and use Aufbau principle, Hund’s rule and
Pauli exclusion principle
b) Apply rules in (a) to fill electrons into atomic
orbitals.
c) Write the electronic configuration of an atom and
monostomic ions by using spdf notation .
d) Explain the anomalous electronic configurations of
chromium and copper.

72
Representing Electronic Configuration
Method 1: Orbital diagram
1s 2s 2p

8 O: box

platform

Concentric circle

Method 2: spdf notation

8 O: 1s 2 2s 2 2p 4 73
 Rules for Assigning Electrons to Orbitals

i) Aufbau Principle
Electrons fill the lowest energy orbitals first and other
orbitals in order of ascending energy.
The order of filling orbitals is:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s

1s 1s 2s 2p

2s 2p
3s 3p 3d
4s 4p 4d 4f
74

5s 5p 5d 5f
Relative Energy Level of Atomic Orbitals
4d
5s
4p

3d
n=4 4s n=4 4s 4p 4d
energy

energy
3p
n=3 3s n=3 3s 3p 3d

2p
n=2 2s n=2 2s 2p

n=1 1s n=1 1s

Orbital energy levels Orbital energy levels

in a many-electron atom in the H atom 75
 Rules for Assigning Electrons to Orbitals

ii) Pauli Exclusion Principle

No two electrons in an atom can have the same four
quantum numbers (n, , m, s)

1s
n  m s
1
e(a) (1 , 0 , 0 , 2
)
a b c 1
e(b) (1 , 0 , 0 , )
2
1
e(c) 1 0 0
2 76
 Rules for Assigning Electrons to Orbitals

iii) Hund’s Rule

Only when all the degenerate orbitals (a group of
orbitals of identical energy e.g. three p-orbitals and five d-
orbitals) contain an electron do the electrons begin to
occupy these orbitals in pairs. The electrons in half-filled
orbitals have the same spins, that is, parallel spins.

2p

77
Exercise
Indicate which of the following orbital diagrams are
acceptable or unacceptable for an atom in ground state.
Explain what mistakes have been made in each and draw
the correct orbital diagram:

1s 2s 2p 1s 2s 2p

1s 2s 2p 1s 2s 2p

1s 2s 2p 1s 2s 2p

78
Exercise
Draw ‘electrons-in-boxes’ diagram of the electronic
configuration of titanium, Ti (Z = 22). Also, write the ground-
state electronic configurations for Ti and Ti2+ ion.

79
 IMPORTANT!
 In an empty atom, the 4s orbital has a lower
energy compared to that of the 3d orbital. That is
why electrons fill the 4s orbital first before filling
the 3d orbital.

 However, once electron/s is/are added to the 3d

orbital, the 4s electrons are repelled to a higher
energy level. The 3d orbitals now have lower
energy than 4s.

80
 Points to remember
 The electronic configuration of atom or monatomic ion at
ground state
 Distribution of electrons obeys Aufbau principle, Pauli
exclusion principle and Hund’s rule
 Each atomic orbital can only accommodate a maximum of 2
electrons
 Atomic orbital is a 3-D region in space around the nucleus
where there is a high probability of finding an electron.
 Assigning electrons to subshells
s-orbital  a max of 2 electrons (ns2)
p-orbitals  a max of 6 electrons (np6)
d-orbitals  a max of 10 electrons (nd10) 81
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.

Element Expected Observed/actual

Cr (Z=24) [Ar] 3d4 4s2 [Ar] 3d5 4s1

Cu (Z=29) [Ar] 3d9 4s2 [Ar] 3d10 4s1

82
Chromium predicted orbital notation

24Cr : 18[Ar]

3d 4s

The actual orbital notation

24Cr : 18[Ar]

3d 4s
Half filled orbital is more stable
(possesses an extra, added stability) 83
Copper predicted orbital notation

 Cu : [Ar]

3d 4s

The actual orbital notation

 Cu : [Ar]

3d 4s
Full filled orbital is more stable
(possesses an extra, added stability) 84
 z = 21

z = 30
85
Exercise

Write the ground-state electronic configuration and

explain the anomalous case for Cr (Z=24) and Cu ( Z=29)

86
 Writing Electronic Configuration for Negative Ion

Add electron according to Aufbau Principle.

Example:
i. Cl-

ii. O2-
 Writing Electronic Configuration for Positive Ions

Remove electron from the outermost orbital

(largest value of n)

Example:
i. Mg2+

ii. K+

iii. Fe2+