1

CHAPTER 6


ELECTRONIC
STRUCTURE OF
ATOMS




2
CONTENT
6.1 The wave nature of light
6.2 Quantized Energy and Photons
6.3 Bohrs Model of the Hydrogen Atom
6.4 The Wave Behaviour of Matter
6.5 Quantum Mechanics and Atomic Orbitals
6.6 Representations of Orbitals
6.7 Orbital in Many-Electron Atoms
6.8 Electron Configurations
6.9 Electron Configurations and The Periodic
Table




3
Learning Outcomes
- should be able to name the orbital of an
electron from the n, l, m
l
values given
- Able to write the electronic configuration of
any element
- Able to calculate the energy associated with
electron movement in atom (Bohr model)


4
INTRODUCTION
In the Periodic Table, elements that exhibit
similar properties are placed together in the
same column.
E.g.
i. Na and K (Group 1A) are soft reactive metals.
ii. He and Ne (Group 8A) are unreactive gases.

The fundamental reason for this similarity lies
on the behaviour of electrons in atoms.




5
Cont: INTRODUCTION
When atoms react it is the electrons that
interact (share/transfer electron).

Therefore, we must understand the behaviour
of electrons.

Arrangement of electrons in atom is called
electronic structure (configuration).




6
Cont: INTRODUCTION
ELECTRONIC STRUCTURE

Electronic structure refers to:

- No. of electrons that an atom possesses.
- Electron distribution around the atom.
- Electrons energies.





7
6.1 The Wave Nature of Light

When you sense the warmth of a fire,
you are feeling what scientists call
radiation or electromagnetic radiation.

Electromagnetic radiation carries energy
through space and is therefore also
known as radiant energy.






8
Cont: 6.1 The Wave Nature of
Light
Fire gives off light (visible radiation) and
heat (thermal radiation).
Both types of electromagnetic radiation
exist in the form of electromagnetic
waves.
All waves have wavelength, (lambda)
and amplitude, A and frequency, u (nu)
characteristics.




9







10
Cont: 6.1 The Wave Nature of
Light
Frequency
The frequency u (nu) of a wave is the
number of cycles that pass through a
given point in one second.

Unit of frequency is Hertz (Hz).

1 Hz = 1 cycle per second or (1 s
-1
).




11
Cont: 6.1 The Wave Nature of
Light
Wavelength
The wavelength, (lambda) is the
distance between successive peaks (or
valleys)

Unit of depends on the type of
radiation.





12
Cont: 6.1 The Wave Nature of
Light
Common units for Electromagnetic Radiation:
unit symbol length(m) type of radiation
Angstrom 10
-10
x ray
nanometer nm 10
-9
UV, visible
micrometer m 10
-6
IR
milimeter mm 10
-3
IR
centimeter cm 10
-2
microwave
meter m 1 TV, radio





13







14
Cont: 6.1 The Wave Nature of
Light
Relationship between and u:

u = c / or c = u

where c is the speed of light, 3.00 10
8
ms
-1
.



15
Example 1
Calculate the wavelength of an electromagnetic
radiation that has a frequency of 9.22 10
17
s
-1
.

c = u ; = c / u
= 3.00 10
8
ms
-1

9.22 10
17
s
-1


= 3.25 10
-10
m




16
6.2 Quantized Energy and Photons
3 Phenomena involving matter and light were
confounding to physicists of the early 20th
century:

a) Blackbody radiation
b) The photoelectric effect
c) Line spectra





17
6.2.1 Blackbody Radiation
When solids are heated, they emit radiation.

Eg:
1000 K, heat a coal soft red glow
1500 K, light is brighter and more orange
> 2000 K, light brighter and whiter





18
Cont: 6.2.1 Blackbody
Radiation
Max Planck (1900) proposed that the minimum
amount of radiant energy (E) that an object
can release or absorb is related to the
frequency (u ) of the radiation.
E=hv where h = Plancks constant

The minimum (smallest quantity) energy that
can be emitted or absorbed as electromagnetic
radiation is called a quantum of energy.




19
Cont: 6.2.1 Blackbody
Radiation

For a single quantum:
E = hu
h = Plancks constant
= 6.63 10
-34
Joule-seconds (Js)
u = frequency





20
Cont: 6.2.1 Blackbody
Radiation
Plancks quantum theory

energy is quantised (discreet values)

always emitted or absorbed in whole-
number multiples of hu, e.g. hu, 2hu,
3hu...






21
Example 2
Calculate the smallest increment of energy, the
quantum of energy, that an object can absorb
from yellow light whose wavelength is 589 nm.
u = c/
= 3.00 10
8
ms
-1

589 10
-9
m
= 5.09 10
14
s
-1
E = hu
= (6.63 10
-34
Js) (5.09 10
14
s
-1
)
= 3.37 10
-19
J




22
Cont: 6.2.1 Blackbody
Radiation
Plancks theory tells us that an atom or
molecule emitting or absorbing radiation whose
wavelength is 589 nm cannot lose or gain
energy by radiation except in multiples of 3.37
10
-19
J. (1 hu = 3.37 10
-19
J)
If one quantum of radiant energy supplies 3.37
10
-19
J, then one mole of these quanta will
supply:
(6.022 10
23
quanta) (3.37 10
-19
J / quantum )
= 2.03 10
5
J.




23
6.2.2 The Photoelectric Effect
Albert Einstein used the quantum theory to
explain the photoelectric effect.

Photoelectric effect - light shinning on a clean
metal surface causes the surface to emit
electrons.

Einstein proposed that a beam of light consists
of a collection of small particles of energy, called
photons.




24
Cont: 6.2.2 The Photoelectric
Effect
Each photon must have an energy proportional
to the frequency of the light thus E = hu.

When a photon strikes the metal, its energy is
transferred to an electron in the metal.

The electrons will only be ejected once the
threshold frequency is reached.






25
Cont: 6.2.2 The Photoelectric
Effect

An electron is ejected if it gains sufficient
energy (energy threshold) to overcome the
forces binding the electron (attractive forces
that hold it within the metal).

If a photon has more than the minimum energy
required to free an electron, the excess
appears as the kinetic energy of the emitted
electron.




26





QUESTION
It requires 183.7 kJ/mol to eject electrons from cesium
metal.
i. What is the minimum frequency of light necessary
to emit electrons from cesium via photoelectric
effect?
ii. What is the wavelength of this light?
iii. If cesium is irradiated with light of 416 nm, what is
the maximum possible kinetic energy of the emitted
electrons?



27


28
6.3 Bohrs Model of The
Hydrogen Atom
6.3.1 Line Spectra

Radiation composed of one wavelength is
called monochromatic.
Most radiation sources consist of many
different wavelengths.
Dispersion of radiation into its component
wavelengths produces a spectrum.




29
Cont: 6.3.1 Line Spectra

A spectrum from white light can be
separated into a continuous range of
colours (rainbow) covering all wavelengths
called continuous spectrum.






30
Cont: 6.3.1 Line Spectra

When different gases are placed in a tube,
under reduced pressure and high voltage, the
gases emit different colours of light



When these lights are passed through a prism,
discrete lines are observed- line spectrum.



H
2
(purple), Ne (red-orange), Na vapor
(yellow), N
2
(orange), Hg vapor (blue)


31







32
6.3.2 Bohrs Model
Niels Bohr proposed a model for the hydrogen
atom that enabled scientists to explain
hydrogen line spectrum.
Bohr put forward 3 postulates:
An electron in an atom is allowed certain
energies known as stationary states (orbits).
Radiation and absorption of photons is due to
changes in stationary states.
An electron moves in circular orbits (allowed
energy) around the nucleus and does not
spiral into the nucleus.




33
S

A





34
Cont: 6.3.2 Bohrs Model
In this model, the energy of the hydrogen atom, E,
depends on the value of a number, n, called the
principal quantum number { n is a positive integer:
n = 1,2,3........}
E
n
= (-hcR
H
)
R
H
= Rydberg constant = 1.10 10
7
m
-1

h = Plancks constant, c = speed of light

Therefore: E
n
= (-2.18x10
-18
J)
The energies of the electron of a hydrogen atom
are negative for all values of n.
|
.
|

\
|
2
n
1
|
.
|

\
|
2
n
1


35
Cont: 6.3.2 Bohrs Model
The lower (more negative) the energy is,
the more stable the atom will be.

The energy is lowest (most negative) for
n = 1; ground state.

Other values of n correspond to excited
states of the atom.




36
Cont: 6.3.2 Bohrs Model
Radius of the stationary states (orbits)
increases as n increases and is proportion to n
2
.

The radius of the orbit n=2 is 2
2
=4 times
larger than the radius of the orbit for n=1.

When n=, (the highest energy state), E=0
indicating that electron is removed from the
nucleus.


37
Cont: 6.3.2 Bohrs Model
When an electron moves from a lower (more
negative) energy state to a higher (less
negative) energy state, light is absorbed.

When an electron moves from a higher energy
state to a lower energy state, light is emitted.

Bohrs model is applicable only for atoms or
ions with a single electron (H, He
+
and Li
2+
)


38
Cont: 6.3.2 Bohrs Model
E = E
f
- E
i
where E
f
= final state energy
E
i
=

initial state energy




where n
i
= initial state quantum no.
n
f
= final state quantum no.
(n
i
> n
f
, energy is emitted, v has a negative value)
(n
f
> n
i
, energy is absorbed, v has a positive value)
|
|
.
|

\
|
= A

2
i
2
f
18
n
1
n
1
J 10 x 18 2 E .
|
|
.
|

\
|
=

2
18
1
10 18 . 2
i
i
n
J E


39
Cont: 6.3.2 Bohrs Model
Calculation (n = 2 to n = 3)





J E
J E
n n
hcR E
i f
H
19
2 2
18
2 2
10 03 . 3
2
1
3
1
10 18 . 2
1 1

= A
|
.
|

\
|
= A
|
|
.
|

\
|
= A


40
Cont: 6.3.2 Bohrs Model
Cont: Calculation (n = 2 to n = 3)







One of the wavelengths observed in
hydrogen line spectrum.


( )( )
nm
m
J
s m s J
E
hc
656
10 56 . 6
10 03 . 3
/ 10 00 . 3 . 10 63 . 6
7
19
8 34
=
=


=
=

4
6
P
r
i
n
c
i
p
a
l

q
u
a
n
t
u
m

n
u
m
b
e
r
,

n

E
n
e
r
g
y

1
2
3
5

-hcR
H
-1/4hcR
H
-1/9hcR
H
-1/16hcR
H


42
6.3.3 Summary of Atomic Model
i. First orbit has n = 1 (closest to the nucleus).
ii. The furthest orbit has n = and corresponds to
E = 0
iii. Electrons can move between orbits by absorbing
or emitting energy in quanta (hu, 2hu, 3hu)
iv. Emission or absorption of radiant energy from a
hydrogen atom occurs when an electron moves
from one orbit to another.




43
Cont: 6.3.3 Summary of Atomic
Model
v. If the electron transfer from an initial state with
energy E
i
to a final state with energy E
f
:
AE = E
f
- E
i
where E = hu = -hcR
H
(1/n
2
)



vi. When n
f
> n
i
, energy is absorbed, u is positive.
vii. When n
f
< n
i
, energy is emitted, u is negative.


|
|
.
|

\
|
=
|
|
.
|

\
|
= A

2
f
2
i
18
2
i
2
f
18
n
1
n
1
J 10 x 18 2
n
1
n
1
J 10 x 18 2 E . .


44
Cont: 6.3.3 Summary of Atomic
Model

viii. If a calculated frequency is 2.5 10
15
s
-1
, that
means that light of frequency 2.5 10
15
s
-1
is
absorbed during the transition.

ix. If a calculated frequency is -2.5 10
15
s
-1
, that
means that light of frequency 2.5 10
15
s
-1
is
emitted during the transition.





45
Example 3

What are the postulates of Niels Bohrs
model for the hydrogen atom?






46
Example 3 (Answer)
The postulates are:
An electron moves in a circular path about the
nucleus and does not spiral into the nucleus.
The energy of an electron can have only certain
allowed values; its energy is quantized.
An electron can move from one circular path to
another circular path only when it absorbs or
emits a photon.




47
Example 4

1.What is the meaning of the negative sign in the
equation En = -hcR
H
(1/n
2
)?

2.What is an excited state?

3.When an atom is ionised, what is the final
principal quantum number of the electron?





48
Example 4 (Answer)
Zero point of the atoms energy is when the
electron is completely removed from the
nucleus. Thus E = 0 when n = , so E < 0 for any
n value smaller than .
Any orbit of the hydrogen atom with n 2 is
considered a higher energy orbit and is said to
be an excited state.
Ionisation corresponds to a transition to a final
state of n =




49
6.4 The Wave Behaviour of
Matter

Radiation appears to have either a wavelike or
particlelike (photon) character.

If radiant energy could, under appropriate
conditions, behave as though it were a stream
of particles, could matter, under appropriate
conditions, possibly show the properties of a
wave?





50
Cont: 6.4 The Wave Behaviour
of Matter

Using Einsteins and Plancks equations, Louis de
Broglie derived:
= h h = Plancks constant
mv v = velocity
m = mass

He proposed that the characteristic
wavelength of the electron or of any other
particle depends on its mass, m, and velocity, v;
where the quantity mv is called momentum.





51
6.4.1 Heisenberg Uncertainty
Principle

This concept of waves and particles applies to
low mass, high speed objects.
Discovery of the wave properties of the
electron led to Heisenbergs uncertainty
principle, which indicates that the position and
momentum of an electron cannot both be known
with absolute certainty simultaneously.
Thus it is not appropriate to imagine the
electrons as moving in well-defined circular
orbits about the nucleus.




52
6.5 Quantum Mechanics and
Atomic Orbitals
Erwin Schrdinger proposed the wavefunction
equation , (psi) which contains both wave and
particle terms.
The location of the electron cannot be
determined exactly but the probability of it
being at a particular position is given by the
probability density,
2
.
His work opened a new way of dealing with
subatomic particles known as:
Quantum mechanics or wave mechanics.




53
Cont: 6.5 Quantum Mechanics
and Atomic Orbitals
Note:

Bohrs model - the electron is in a circular orbit
of same particular radius about the nucleus.

In quantum mechanics - the electrons exact
location cannot be determined but the
probability of finding an electron at a given
point in space can be calculated.




54
6.5.1 Orbitals and Quantum
Numbers
Solving the Schrdingers equation will give us
wave functions and energies for the wave
functions.

These allowed wave functions are called
orbitals.

Each orbital describes a specific distribution
of electron density in space.



Light + interaction with matter
(blackbody radiation, photoelectric effect, line spectra)





55
Light + interaction with matter
(blackbody radiation, photoelectric effect, line spectra)

Quantum theory
(Bohrs model, wave behaviour of matter, Heisenberg
Uncertainty Principle)




56
Light + interaction with matter
(blackbody radiation, photoelectric effect, line spectra)

Quantum theory
(Bohrs model, wave behaviour of matter, Heisenberg
Uncertainty Principle)

Quantum Mechanics
(involve math, calculations, equations)



57
Light + interaction with matter
(blackbody radiation, photoelectric effect, line spectra)

Quantum theory
(Bohrs model, wave behaviour of matter, Heisenberg
Uncertainty Principle)

Quantum Mechanics
(involve math, calc, equations)

QUANTUM NUMBER
(tell us how to write electron configuration)

58


59
Cont: 6.5.1 Orbitals and
Quantum Numbers
In Quantum Mechanics, the motion of an
electron about its nucleus and its energy is
characterised by 4 quantum numbers to
describe an orbital.

n - principal quantum number
l - second quantum number/azimuthal
quantum number
m
l
- magnetic quantum number
m
s
electron spin quantum number




60
1. The principal Quantum
Number, n
n = 1, 2, 3.. (positive integer)
Represents the main energy levels for the
electron as a shell in space where the
probability of finding an electron is high.
As n increases:
- the orbital becomes larger
- the electron is further away from the nucleus
- the electron has higher energy (less tightly
bound to the nucleus)




61
2. The Second Quantum Number or
the Azimuthal Quantum Number, l

l = (0, 1, 2, 3,......n -1) for each value of n.

Defines the shape of orbital.

Specifies subenergy levels within the main
energy levels called subshells.

Subshell s, p, d and f are designated by the l
values of 0, 1, 2 and 3, respectively.






62
3. The Magnetic Quantum
Number, m
l
Describe the orientation of a single atomic
orbital in space.
The number of different permissible
orientations of an orbital depends on the l
value of a particular orbital.
The m
l
quantum number has permissible
values of -l to +l, including zero.




63
Cont: 3. The Magnetic Quantum
Number, m
l
Eg.
when l = 0, only one allowed value for m
l

which is 0 (zero).

when l = 1, three permissible values for m
l

which are -1, 0, +1

For a given value of l, there are (2l + 1) values
of m
l
.




64
4. The Electron Spin Quantum
Number, m
s
It was postulated that electrons have an
intrinsic property called electron spin, given by
the electron spin quantum number, m
s
.

The values: - , + (two allowed spin
directions)

The spin quantum number has minor effect on
the energy of an electron.



65
Cont: 4. The Electron Spin
Quantum Number, m
s
Pauli exclusion principle states that no two
electrons in an atom can have the same set of
four quantum numbers (n, l, m
l
, m
s
)

This indicates that each orbital can only be
occupied the most by two electrons of
opposite spin.


66
6.5.2 Summary of Quantum
Numbers
The collection of orbitals with the same value
of n is called an electron shell.

Eg:
All orbitals that have n = 3 are said to be in
the third shell.

The set of orbitals that have the same n and l
values is called a subshell.





67
Cont: 6.5.2 Summary of
Quantum Numbers
The shell n consists of exactly n subshells.

Each subshell has value l from 0 to n-1.

First shell n =1; consists of one subshell 1s (l = 0)




68
Cont: 6.5.2 Summary of
Quantum Numbers
Second shell n = 2; consists of two subshells 2s
(l = 0) and 2p (l = 1)

Third shell n = 3; consists of three subshells 3s
(l = 0), 3p (l = 1), and 3d (l = 2)

Forth shell n = 4; consists of four subshells 4s
(l = 0), 4p (l = 1), 4d (l = 2) and 4f (l = 3)




69
Cont: 6.5.2 Summary of
Quantum Numbers
Each subshell consists of a specific number of
orbitals.

For l value, there are (2l + 1) allowed values of
m
l
.

Each orbital corresponds to a different allowed
value of m
l
.




70
Cont: 6.5.2 Summary of
Quantum Numbers
Eg. Subshell s ( l = 0)
consist of one orbital = (2l + 1)
= ( 2(l) + 1)
= 1
Eg. Subshell p (l = 1)
consist of three orbitals = (2(l) + 1)
= 3 and so forth.





71
Cont: 6.5.2 Summary of
Quantum Numbers
Total no of orbital in a shell is n
2
.

n total no of orbitals in shell
1 1
2 4
3 9
4 16





n
Possible
Values of l
Subshell
Designation
Possible
Values of m
l

Number
of orbitals
in
Subshell
Total
Number of
Orbitals in
Shell
1
2


3


4
0
0
1

0
1
2
0
1
2
3

1s
2s
2p

3s
3p
3d
4s
4p
4d
4f

0
0
1,0,-1

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

1
3
5
1
3
5
7

1

4



9



16
SHELL SUBSHELL ORBITAL


73
Example 5
Write the shorthand notation (for eg 2s)
for the orbitals described by the following
quantum numbers:

a) n = 2, l = 1, m
l
= 0
b) n =3, l = 2, m
l
= 1
c) n = 4, l = 3, m
l
= 2




74
Example 5 (Answer)
a) n = 2
l = 1 corresponds to p orbital.
the orbital designation is 2p
m
l
= 0 could be 2p
x
or 2p
y
or 2p
z


b) n = 3
l = 2 corresponds to d orbital.
the orbital designation is 3d.
m
l
= 1 could be one of the 5 orbitals.




75
Example 5 (Answer)
c) n = 4
l = 3 correspond to f orbital.
the orbital designation is 4f.
m
l
= 2 could be one of the 7 orbitals.




76
Example 6
Why is it not possible for a hydrogen orbital to have
the quantum numbers n =3, l = 2, m
l
= 3 associated
with it?



77
Example 6
Why is it not possible for a hydrogen orbital to have
the quantum numbers n =3, l = 2, m
l
= 3 associated
with it?
For a given l value only certain m
l
values are
allowed.
If n = 3; l = 0, 1, 2 (as l = 0 to n-1)
m
l
= l to -l
= 2, 1, 0, -1, -2

Thus m
l
= 3 is not possible for a hydrogen orbital
with an l = 2 value.




78
Example 7
Which of the following is a correct set of
quantum numbers for an electron in a 3d
orbital?

A. n = 3, l = 0, m
l
= -1
B. n = 3, l = 1, m
l
= +3
C. n = 3, l = 2, m
l
= 0
D. n = 3, l = 3, m
l
= +2




79
Solution
n

l

m
l


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


80
6.6 Representations of Orbitals
6.6.1 The s Orbitals

The s orbital is spherical.
As n increases, the s-orbitals get larger.
1s orbital is the lowest-energy orbital.
The intermediate regions where
2
is zero are
called nodes.
A node is a region in space where the
probability of finding an electron is zero.
No. of nodes increases as n increases.




81
6.6 Representations of Orbitals
6.6.1 The s Orbitals

The s orbital is spherical.
As n increases, the s-orbitals get larger.
1s orbital is the lowest-energy orbital.
The intermediate regions where
2
is zero are
called nodes.
A node is a region in space where the
probability of finding an electron is zero.
No. of nodes increases as n increases.




82
6.6.2 The p Orbital
There are three p-orbitals ; p
x
, p
y
and p
z
.
The letters correspond to allowed values of m
l
of -
1, 0 and +1.
Each shell beginning with n = 2 has three p orbitals.
n = 2 ; l = 0, 1 (s and p orbitals)
m
l
= 0 ; -1, 0, +1
| | | |
2s 2p
x
2p
y
2p
z
Size of p orbitals increases as n increases.
All p orbitals have a node at the nucleus.




83
C
k



84
6.6.3 The d and f Orbitals
When n 3, we encounter the d orbitals (l = 2)
When n 4, we encounter the f orbitals (l = 3)
There are 5d and 7f - orbitals.
n = 4, l = 0, 1, 2, 3,
= s, p, d, f

For d orbital l = 2, m
l
= -2, -1, 0, 1, 2 (5 orbitals)
For f orbital l = 3, m
l
= -3, -2, -1, 0, 1, 2, 3
(7 orbitals)




85
Cont: 6.6.3 The d and f
Orbitals

Three of the d-orbitals lie in a plane bisecting
the x, y and z axes (d
xy
, d
yz
, d
xz
).

Two of the d-orbitals lie in a plane aligned along
the x, y and z axes (d
x
2-
y
2, d
z
2).

f orbitals will not be discussed here.



86


87
C
k



88
C
k



89
6.7 Orbitals in Many-Electron
Atoms
In hydrogen, the energy of an orbital depends
only on its principal quantum number, n (for
n=3; 3s, 3p and 3d subshells have the same
energy).

In many-electron atom, the electron-electron
repulsions cause different subshells to be at
different energies although they are from the
same principal quantum number.






90



91


92
k



93
6.7.1 Effective Nuclear Charge
(Screening Effect)
In many-electron atom, each electron is
simultaneously:
i. Attracted to the nucleus (positively charged).
ii. Repelled by other electrons.

We can estimate individual electron energy by
considering how it interacts with the average
environment created by the nucleus and other
electrons.





94
Cont: 6.7.1 Effective Nuclear
Charge (Screening Effect)
Any electron density between the nucleus and the
electron of interest will reduce the nuclear charge
acting on that electron.

Net positive charge attracting the electron is
called effective nuclear charge, Z
eff
.
Z
eff
= Z - S
Z = number of protons
S = average number of electrons




95
C
k



96
Cont: 6.7.1 Effective Nuclear
Charge (Screening Effect)
The positive charge experienced by outer-shell
electrons is always less than the full nuclear
charge.

Reasons:
i. The inner-shell electrons partly offset the positive
charge of the nucleus
ii. The inner electrons shield the outer electron from
the full charge of the nucleus :screening effect
(or shielding effect)




97
6.7.2 Energies of Orbitals
As we move outward from the nucleus, the
screening effect depends on its electron
distribution.

For a given value of n, electron distribution
differs for each subshell.






98
Cont: 6.7.2 Energies of Orbitals
Eg : n = 3 (3s, 3p, 3d)
- The closeness of the electrons to the nucleus
in the orbitals decrease:
3s > 3p> 3d
- As a result, the shielding effect experienced
by the electrons increase:
3s < 3p< 3d
- Therefore, the Z
eff
experienced by the
electrons in the orbitals decrease:
3s > 3p> 3d


99
Cont: 6.7.2 Energies of Orbitals
Generally, in a many-electron atom, for a
given value of n, Z
eff
decreases with
increasing value of l.
The energy of an electron depends on Z
eff
.
All orbitals of a given subshell, such as 3d
orbitals have the same energy.
Orbitals with the same energy are said to be
degenerate.




100
6.8 Electron Configuration
The way in which the electrons are
distributed or arranged among orbitals of
various energy levels around an atomic
nucleus.
The most stable or ground state of the
electron configuration : the electrons in the
lowest possible energy states.
The most stable ground state is 1s orbital.
Pauli exclusion principal : there can only be a
maximum of two electrons in any single
orbital.




101
Cont: 6.8 Electron Configuration
The orbitals are filled in the order of increasing
energy - 2 electrons per orbital.
The maximum number of electrons which can
accommodate in each shell in an atom is defined
by different sets of the four quantum numbers
and is 2n
2
.

Eg: There can only be maximum of 2 electrons for
the first principal shell, n =1 (n=2, maximum
electrons=8; n=3, maximum electrons=18).




102
Cont: 6.8 Electron Configuration
Electron configurations are written that lists
the principal quantum number first, followed by
an orbital letter s, p, d or f.
The order in which the electrons fill up the
orbitals is as follows:
1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6
5s
2
4d
10

5p
6
6s
2
4f
14
5d
10
6p
6
7s
2
5f
14
6d
10
7p
6

A convenient way to memorise this order is by
following the arrows from tail to head.





103
C
k

104
105
106


107
Cont: 6.8 Electron Configuration
We can also show the arrangement of the
electrons as:

Hydrogen 1s
1
-

Helium 1s
2
-

Lithium 1s
2
2s
1
-

This is called an orbital diagram.




108
Cont: 6.8 Electron Configuration
Orbital diagram.
Each orbital is represented by a box.
Each electron is represented by a half arrow.


m
s
= + m
s
= -
(spin-up) (spin-down)





109
6.8.1 Periods 1, 2 and 3
How the electron configurations of the
elements change as we move from element to
element across the Periodic Table.
All the three 2p orbitals are of equal energy.
For carbon, the 6th electron must go into 2p
orbital.


1s 2s
2p
?


110
Cont: 6.8.1 Periods 1, 2 and 3
Follow Hunds Rule - for degenerate orbitals,
the lowest energy is attained when the
number of electrons with the same spin is
maximised.
This means that the orbitals of a subshell must
be occupied singly and with parallel spins
before they can be occupied in pairs.


1s 2s
2p


111
Cont: 6.8.1 Periods 1, 2 and 3
For Nitrogen we have 7 electrons.
The orbital diagram will be as follows:




- The electrons will occupy orbitals singly to the
maximum extent possible to achieve its lowest
energy - minimising electron-electron repulsion.


1s 2s
2p


112
Cont: 6.8.1 Periods 1, 2 and 3
As for sodium (Z = 11), it has a single 3s electron
beyond the stable configuration of neon.




Abbreviation of the electron configuration of
sodium is as follows:
Na [Ne] 3s
1




1 s 2 s
2 p
3s


113
Cont: 6.8.1 Periods 1, 2 and 3
Symbol [Ne] represents the electron configuration
of the 10 electrons of Neon
1s
2
2s
2
2p
6
.
This system helps to focus on the outermost
electrons of the atom.
The outer electrons are the ones largely
responsible for the chemical behaviour of an
element.




114




115
Cont: 6.8.1 Periods 1, 2 and 3
Eg : Li [He] 2s
1


Li and Na have the same type of outer-shell
electron configuration.
The outer-shell electrons are often referred
to as valence electrons.
The electrons in the inner shells are the core
electrons.
All the members of the alkali metal group (1A)
have a single s electron beyond a noble gas
configuration.




116
6.8.2 Period 4 and Beyond
The next element following Argon in the
Periodic Table is potassium (K).

Argons electron configuration is 1s
2
2s
2
2p
6

3s
2
3p
6
.

Potassium is a member of alkali metal group ie
K has a single s electron beyond Argon
configuration.

This means that the highest-energy electron
has not gone into 3d orbital.




117
Cont: 6.8.2 Period 4 and Beyond
4s orbital is lower in energy than that of 3d.

4s orbital is filled first followed by 3d orbitals.
Eg:

19
K - 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1

(
19
K - [Ar] 4s
1
)

20
Ca - 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2

(
20
Ca - [Ar] 4s
2
)







118
Cont: 6.8.2 Period 4 and Beyond


21
Sc - 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
1

(
21
Sc - [Ar] 4s
2
3d
1
)
30
Zn - [Ar] 4s
2
3d
10


*Sc represents the start of transition metal series

Follow Hunds Rule, electrons are added to the
3d orbitals singly until all 5 orbitals have one
electron each.




3d


119
Cont: 6.8.2 Period 4 and Beyond
Additional electrons are placed in the 3d
orbitals with spin pairing.




Electrons having opposite spins are said to be
paired when they are in the same orbital.

Upon completion of 3d transition series, the 4p
orbitals begin to be filled.


3d


120
6.9 Electron Configurations and
The Periodic Table
Electron configuration of the elements are
related to their location in the Periodic Table.

Elements with the same pattern of valence
electron configuration are arranged in the same
column.

Eg: All 2A elements have ns
2
outer configuration.

All 3A elements have ns
2
np
1
outer configuration.




121
Cont
4



122
Cont: 6.9 Electron Configurations
and The Periodic Table
The total number of orbitals in each shell is equal to
n
2
: 1, 4, 9 or 16.
The total number of electrons a particular shell can
accommodate is 2n
2
electrons : 2, 8, 18 or 32.
Consider the Periodic Table:
- First row has 2 elements.
- 2nd and 3rd rows have 8 elements.
- 4th and 5th rows have 18 elements.
- 6th row has 32 elements (including lanthanides).
Therefore, the Periodic Table is the best guide to
the order in which orbitals are filled.




123
Cont: 6.9 Electron Configurations
and The Periodic Table
Element can be grouped in terms of the type of
orbital into which the electrons are placed.
1A and 2A elements (s-block) - the outer-shell s
orbitals are being filled.
3A to 8A elements (p-block) - the outer most p
orbitals are being filled.
s-block and p-block contain the representative (or
main-group) elements.
Transition metals (d-block) - the outer most d
orbitals are being filled.




124
Cont: ELECTRON CONFIGURATIONS AND THE
PERIODIC TABLE
4



125
SUMMARY AND KEY TERMS
Electrons in an atom show two intrinsic spin
orientations in the presence of a magnetic
field.
The two spin orientations are in opposite
directions and are quantized.
Electron spin is defined by the electron-spin
quantum number, m
s
, which has two possible
values, m
s
= +1/2 , m
s
= -1/2
Pauli exclusion principle states that:
No two electrons in an atom can have the same
set of four quantum numbers n, l, m
l
and m
s
.




126
Cont: SUMMARY AND KEY
TERMS
An orbital can hold a maximum of two electrons
and these electrons must have opposite spins.

Subshells (for example 2s and 2p) do not have
the same energies as they do in a hydrogen
atom.

Orbitals within a subshell (for example 2px, 2py
and 2pz) possess the same energy.




127
Cont: SUMMARY AND KEY
TERMS
Electrons occupy orbitals in order of increasing
energy.

All orbitals that are equal in energy (degenerate)
are filled with electron first, before the next level
of energy begins to fill up.

(A few exceptions exist : Cr and Cu)





128
Example 8
Write electron configuration for Ti (atomic no.= 22
Solution:
Step 1
2
He : 1s
2


10
Ne : 1s
2
2s
2
2p
6


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


36
Kr : 1s
2
2s
2
2p
6
3s
2
3p
6
4s
2
3d
10
4p
6

Ar : 18 electrons
Ti : 22 electrons [Ar] + 4 electrons
[Ar] 4s
2
3d
2






129
Example 8 (cont)
Remember of a few exceptions:


24
Cr : [Ar] 4s
1
3d
5



29
Cu : [Ar] 4s
1
3d
10




47
Ag : [Kr] 5s
1
4d
10





130

END of CHAPTER 6



131