Electronic Configuration

Ochran 2014
 THE BOHR MODEL OF THE ATOM
A small nucleus of protons and neutrons
surrounded by electrons in shells
each shell holding up to a maximum number of electrons
and filled from the first shell outwards
electrons in the first shell being the most strongly held
and therefore at the lowest energy level.

Maximum electrons per shell

1st shell 2
2nd shell 8
3rd shell 18
4th shell 32

The theory couldn’t explain certain detailed aspects of the

chemistry of the elements or their emission spectra.
 SHELLS, SUB-SHELLS AND ENERGY LEVELS
PRINCIPAL SUB SHELLS
QUANTUM
NUMBER OF f A study of First Ionisation Energies
SHELL
d across each period suggested that each
4 ‘shell’ was in fact a group of ‘sub-shells’
INCREASING ENERGY / DISTANCE FROM NUCLEUS

p
at different but similar energy levels.
s
d The electrons in different sub-shells have
3 p different energy levels.
s
Shell 1 contains only an s sub-shell

p Shell 2 contains an s and p sub-shell

2 Shell 3 contains an s, p and d sub-shell
s
Shell 4 contains an s, p, d and f sub-shell

1 s How are electrons arranged within these

sub-shells?
 RULES AND PRINCIPLES ARISING FROM QUANTUM MECHANICS

These four rules govern how electrons are arranged in atoms.

HEISENBERG’S UNCERTAINTY PRINCIPLE

“You cannot determine both the position and momentum of an
electron at the same time.”

PAULI’S EXCLUSION PRINCIPLE

“No two electrons can have the same four quantum numbers.”

THE AFBAU (BUILDING UP) PRINCIPLE

“Electrons enter the lowest available energy level.”

HUND’S RULE OF MAXIMUM MULTIPLICITY

“When in orbitals of equal energy, electrons will try to remain
unpaired.”
 ELECTRONS OCCUPY ORBITALS

An orbital is a region in space

where there is a 95% probability of finding the electron.
(Heisenberg’s Uncertainty Principle)

Orbitals can hold one electron

or two electrons as long as they have opposite spin.
(Pauli Exclusion Principle)

Orbitals have different shapes

depending on which sub-shell they are in.

DO NOT USE THE WORD ORBIT WHEN YOU MEAN AN ORBITAL

 SHAPES OF ORBITALS

One s orbital makes the s sub-shell

spherical
 SHAPES OF ORBITALS

Three p orbitals make the p sub-shell

dumb-bell shaped
 SHAPES OF ORBITALS

Five d orbitals make the d sub-shell

four are double dumb-bell shaped

the other a dumb-bell with a collar
 ORDER OF FILLING ORBITALS
PRINCIPAL
PRINCIPAL
QUANTUM
QUANTUM
SUB
SUBSHELLS
SHELLS Orbitals are filled from the lowest
NUMBER OF
NUMBER OF
SHELL 4f
4f energy level upwards.

INCREASING ENERGY / DISTANCE FROM NUCLEUS

SHELL 4d
4d
44 (The Aufbau Principle)
4p
4p
3d
4s The quantum shells get closer
4s
3 3p together in space as you get
3d
3 3s
3p further from the nucleus.
3s
There is an overlap in the energy
2p
2 levels of the sub-shells of different
2p
2s
2 shells.
2s
The first example occurs when the
4s orbital is filled before the 3d
orbitals because it is at a lower
11 1s
1s energy level.
The 4s orbital is still part of the
forth shell and is physically further
from the nucleus than the 3d sub-
shell.
 ORDER OF FILLING ORBITALS

PRINCIPAL SUB SHELLS

Orbitals are filled from the lowest
QUANTUM energy level upwards.

INCREASING ENERGY / DISTANCE FROM NUCLEUS

NUMBER OF 4f
SHELL 4d (The Aufbau Principle)
4
4p The quantum shells get closer
3d
4s together in space as you get
3 3p further from the nucleus.
3s
There is an overlap in the energy
2p levels of the sub-shells of different
2
2s shells.
The first example occurs when the
4s orbital is filled before the 3d
orbitals because it is at a lower
1 1s
energy level.
The 4s orbital is still part of the
forth shell and is physically further
from the nucleus than the 3d sub-
shell.
 ORDER OF FILLING ORBITALS
PRINCIPAL SUB SHELLS
QUANTUM
NUMBER OF 4f
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4
SHELL 4d HOW TO
4p
3d
REMEMBER
THE FILLING ORDER
4s
3 3p 1s
3s 2s 2p
3s 3p 3d
2p 4s 4p 4d 4f
2
2s 5s 5p 5d 5f
6s 6p 6d
7s 7p

1 1s

The 4s orbital is filled before the 3d orbitals.

 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f The following
4d
sequence will show
4 the ‘building up’ of
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p the electronic
3d structures of the
4s first 36 elements in
3
the periodic table.
3p

3s
Electrons are shown
as half headed
arrows and can spin
2p in one of two
2 directions
2s
s orbitals
p orbitals
1 1s
d orbitals
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
HYDROGEN
4d
4 1s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Hydrogen atoms have
3d
one electron.
4s
3
This goes into a
3p
vacant orbital in the
3s lowest available
energy level.
2p
2
2s

The Aufbau Principle

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
HELIUM
4d
4 1s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Every orbital can
3d
contain 2 electrons,
4s
provided the electrons
3 3p have opposite ‘spins’.
3s The two electrons in a
helium atom can both
go in the 1s orbital.
2p
2
2s
Pauli’s Exclusion Principle

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f

4d
4 LITHIUM
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
1s2 2s1
3d
4s
3 3p Orbitals hold a maximum
of two electrons, so the
3s
third electron in a
lithium atom must go into
2p the next available
2 orbital.
2s
This is the 2s orbital.
An s orbital is lower in
1 1s energy than a p orbital
in the same shell.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
BERYLLIUM
4d
4 1s2 2s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
Beryllium atoms have
3d
four electrons, so
4s
the fourth electron
3 3p pairs up in the 2s
3s orbital.
The 2s sub-shell,
which only contains
2p
2 the 2s orbital, is
2s now full.

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
BORON
4d
4 1s2 2s2 2p1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
As the 2s sub-shell
3d
is now full, the fifth
4s
electron goes into
3 3p one of the three p
3s orbitals in the 2p
sub-shell.
The 2p orbitals are
2p
2 slightly higher in
2s energy than the 2s
orbital but each are
at the same energy
1 1s level, they are
‘degenerate’.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
CARBON
4d
4 1s2 2s2 2p2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
The next electron doesn’t
3 3p pair up with the other 2p
3s electron as there is an
empty orbital available of
the same energy.
2p
2 There is less repulsion
2s between the electrons when
in separate orbitals
resulting in an arrangement
1 1s of lower energy and more
stability.

HUND’S RULE OF MAXIMUM MULTIPLICITY

 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
NITROGEN
4d
4 1s2 2s2 2p3
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The next electron
3d
goes into the vacant
4s
p orbital of the
3 3p same energy.
3s All three electrons
are now unpaired.
2p
2 Less repulsion
2s
Lower energy
More stability.
1 1s

HUND’S RULE OF MAXIMUM MULTIPLICITY

 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
OXYGEN
4d
4 1s2 2s2 2p4
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
With all three orbitals
3 3p
half-filled, the eighth
3s electron in an oxygen atom
must now pair up with one
of the 2p electrons.
2p
2 The repulsion between the
2s two paired electrons raises
their energy level.

1 1s
This explains the drop in
first ionisation energy from
N to O.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
FLUORINE
4d
4 1s2 2s2 2p5
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The electrons
3d
continue to pair up
4s
with those in the
3 3p half-filled orbitals.
3s

2p
2
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
NEON
4d
4 1s2 2s2 2p6
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The electron pairs up
3d
with the one in the last
4s
half-filled p orbital.
3 3p
The three 2p orbitals
3s are now completely
filled, filling the 2p
sub-shell and the shell
2p
2 of principal quantum
2s number 2.
The ‘IG’ electronic
configuration would
1 1s
have been written as
2,8.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
SODIUM - ARGON
4d
4
With the second
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
shell full, the next
3d electron must go into
4s the next available
3 3p orbital with the
lowest energy.
3s
The third shell
contains three sub-
2p shells; s, p and d.
2
2s The one 3s and the
three 3p orbitals are
filled in exactly the
1 1s same way as those in
the 2s and 2p sub
shells.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS
SODIUM - ARGON
4f
Na 1s2 2s2 2p6 3s1
4d Mg 1s2 2s2 2p6 3s2
4
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p Al 1s2 2s2 2p6 3s2 3p1

3d Si 1s2 2s2 2p6 3s2 3p2
4s P 1s2 2s2 2p6 3s2 3p3
3 3p S 1s2 2s2 2p6 3s2 3p4
3s Cl 1s2 2s2 2p6 3s2 3p5
Ar 1s2 2s2 2p6 3s2 3p6

2p
2
2s Remember, Hund’s Rule is
followed. Electrons remain
unpaired if a vacant p orbital is
1 1s available. This provides a lower
energy level as the electrons repel
less than when paired.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
POTASSIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s1
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
The 4s orbital is of a
3 3p
LOWER ENERGY than
3s that of the 3d orbitals.
The 4s gets filled first!
2p
2
2s The Aufbau Principle

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
CALCIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The next electron
3d
pairs up and fills the
4s
4s orbital.
3 3p
All elements with an s1
3s electronic configuration
are in Group 1.
2p All elements with an s2
2 electronic configuration
2s
are in Group 2.
Groups 1 and 2 are
1 1s known together as the
s block. The highest
energy electron is in an
s orbital.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
SCANDIUM 1s2 2s2 2p6 3s2 3p6 4s2 3d1
4d
4
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p There are five d

orbitals. They are
3d
‘degenerate’ i.e. are
4s
at the same energy
3 3p level.
3s So they are each
filled with a single
electron before any is
2p
2 filled with two ‘spin
2s paired’ electrons.

HUND’S RULE OF
MAXIMUM MULTIPLICITY
1 1s

WATCH OUT FOR TWO

SPECIAL CASES !
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
TITANIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d2
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
These are the
4s transition metals
3 3p also known as the
3s d block elements.
The highest
energy electron
2p
2 enters a d orbital
2s

HUND’S RULE OF
MAXIMUM MULTIPLICITY
1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS
VANADIUM 1s2 2s2 2p6 3s2 3p6 4s2 3d3
4f
The 3d orbitals are part
4d
4 of the 3rd shell, which is
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p an inner shell closer to

3d the nucleus than the 4s
4s orbital of the 4th shell.
3 3p Therefore, the atomic
size of d block elements
3s
remains relatively
constant across a
2p period.
2
2s
Nuclear charge is increased by one
proton but is shielded by one inner
shell 3d electron.
1 1s
So, the 4s electrons experience an
approximately unchanged nuclear
attraction across the d block.
 Anomalous Electron Configurations
• A few exceptions to the Aufbau principles
exist. Stable configuration:
– half-filled d shell is stable:
• Cr has [Ar]4s13d5;
• Mo has [Kr] 5s14d5
– filled d subshell is stable:
• Cu has [Ar]4s13d10
• Ag has [Kr]5s14d10.
• Au has [Xe]6s14f145d10
• Exceptions occur with larger elements
where orbital energies are similar.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
CHROMIUM
4d
4 1s2 2s2 2p6 3s2 3p6 4s1 3d5
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
One would expect the
3d
electronic configuration
4s
of the chromium atom
3 3p to be [Ar] 4s2 3d4.
3s The 4s and 3d orbitals
are close in energy.
2p The arrangement of six
2 unpaired electrons has
2s
a lower energy than if
two electrons are
paired (repelling each
1 1s
other) in the 4s
orbital.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
MANGANESE
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d5
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The new electron
3d
goes into the 4s
4s
orbital to restore
3 3p its filled state.
3s

2p
2
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
IRON
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d6
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
3 3p

3s

2p
2
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
COBALT
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d7
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
3 3p

3s

2p
2
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
NICKEL
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d8
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d
4s
3 3p

3s

2p
2
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
COPPER
4d
4 1s2 2s2 2p6 3s2 3p6 4s1 3d10
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
One would expect the
3d
configuration of
4s
chromium atoms to be…
3 3p
[Ar] 4s2 3d9.
3s
However, the actual
arrangement…
2p [Ar] 4s1 3d9
2
2s Is of lower energy and
therefore the stable
arrangement.
1 1s
This can be rationalised
by the symmetry of
the full 3d sub-shell.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
ZINC
4d
4 1s2 2s2 2p6 3s2 3p6 4s2 3d10
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
The electron goes
3d
into the 4s orbital
4s
to restore its
3 3p filled state.
3s The inner 3rd shell
is now complete.
Zn is the last d
2p
2 block element in
2s the 4th period.
The available
orbitals of next
1 1s
highest energy are
the 4p and and
these fill next.
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
GALLIUM - KRYPTON
4d
4
The 4p orbitals are
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p
filled in exactly the
3d same way as the 3p
4s orbitals were.
3 3p These elements are
3s in the p block.
The highest energy
2p
electron is in a p
2 orbital.
2s

1 1s
 THE ELECTRONIC CONFIGURATIONS OF THE FIRST 36 ELEMENTS

4f
GALLIUM - KRYPTON
4d
4 Ga
INCREASING ENERGY / DISTANCE FROM NUCLEUS

4p

3d 1s22s22p63s23p64s23d104p1
4s Ge
3 3p
1s22s22p63s23p64s23d104p1
3s
Or, in shortened form…
As [Ar]4s23d104p3
2p
2
2s
Se [Ar]4s23d104p4
Br [Ar]4s23d104p5

1 1s Kr [Ar]4s23d104p6
H 1s1
ELECTRONIC
He 1s2
CONFIGURATIONS
Li 1s2 2s1
OF ELEMENTS 1-30
Be 1s2 2s2
B 1s2 2s2 2p1
C 1s2 2s2 2p2
N 1s2 2s2 2p3
O
1s2 2s2 2p4
F
1s2 2s2 2p5
Ne
1s2 2s2 2p6
Na
Mg 1s2 2s2 2p6 3s1
Al 1s2 2s2 2p6 3s2
Si 1s2 2s2 2p6 3s2 3p1
P 1s2 2s2 2p6 3s2 3p2
S 1s2 2s2 2p6 3s2 3p3
Cl 1s2 2s2 2p6 3s2 3p4
Ar 1s2 2s2 2p6 3s2 3p5
K 1s2 2s2 2p6 3s2 3p6
Ca 1s2 2s2 2p6 3s2 3p6 4s1
Sc 1s2 2s2 2p6 3s2 3p6 4s2
Ti
1s2 2s2 2p6 3s2 3p6 4s2 3d1
V
1s2 2s2 2p6 3s2 3p6 4s2 3d2
Cr
Mn
1s2 2s2 2p6 3s2 3p6 4s2 3d3
Fe 1s2 2s2 2p6 3s2 3p6 4s1 3d5
Co 1s2 2s2 2p6 3s2 3p6 4s2 3d5
Ni 1s2 2s2 2p6 3s2 3p6 4s2 3d6
Cu 1s2 2s2 2p6 3s2 3p6 4s2 3d7
Zn 1s2 2s2 2p6 3s2 3p6 4s2 3d8
1s2 2s2 2p6 3s2 3p6 4s1 3d10
1s2 2s2 2p6 3s2 3p6 4s2 3d10
 ELECTRONIC CONFIGURATION OF IONS

Positive ions (cations) are formed by removing electrons from atoms.

Negative ions (anions) are formed by adding electrons to atoms.
Electrons are removed first from the occupied orbital of highest
energy.
Ions of s and p block elements are ‘isoelectronic’ with a noble gas
but contain a different number of protons and are charged.

SODIUM
Na 1s2 2s2 2p6 3s1
Na+ 1s2 2s2 2p6 1 electron removed from the 3s orbital
Ne 1s2 2s2 2p6
CHLORINE
Cl 1s2 2s2 2p6 3s2 3p5
Cl- 1s2 2s2 2p6 3s2 3p6 1 electron added to the 3p orbital
Ar 1s2 2s2 2p6 3s2 3p6
 ELECTRONIC CONFIGURATION OF IONS

FIRST ROW TRANSITION METALS

Despite being initially of lower energy and therefore having
been filled first, the energy level of the 4s orbital becomes
higher when the 3d orbitals contain electrons. Due to the
repulsion between electrons in the 3d and 4s sub-shells
Therefore, electrons in the 4s orbital are removed before
any electrons in the 3d orbitals.

TITANIUM
Ti 1s2 2s2 2p6 3s2 3p6 4s2 3d2
Ti+ 1s2 2s2 2p6 3s2 3p6 4s1 3d2
Ti2+ 1s2 2s2 2p6 3s2 3p6 3d2
Ti3+ 1s2 2s2 2p6 3s2 3p6 3d1
Ti4+ 1s2 2s2 2p6 3s2 3p6
References

Nelson 12
Richard Rogers
Nomad 1970