ELECTRONS IN ATOMS

The arrangement of the electrons within each atom determines how that atom interacts with
other atoms and with its surroundings. The electrons are organized into different levels of
energy, and understanding the effects of this arrangement is key to understanding chemistry
itself. We can also make use of these electron levels. For example, causing an electron to move
between energy levels can cause energy to be emitted or absorbed. Sometimes, we can see this
in the form of light.
Sub-shells and Atomic Orbitals
Principle quantum shells
Electrons are arranged outside the nucleus in energy levels or principle quantum shells which
can be denoted as n.
The lowest energy level, n = 1 is closest to the nucleus, the energy level n = 2 is further out, and
so on. The electrons in energy level further away from the nucleus have more energy and held
less tightly by the nucleus. Electrons do not move in fixed circular paths, they occupy a space
called the atomic orbitals.
The total number of electrons that can occupy any principal shell is 2n², where n is the principal
quantum number.
Quantum sub-shells
The principal quantum shells, apart from the first, are split into sub-shells. Each principle
quantum shell contains a different number of sub-shells.
The first energy level contains one sub-shell, the second energy level contains two and so on.
The sub-shells are distinguished by letters s, p, d, f and the energy of electrons in the sub-shells
increases in the order s < p < d < f.

1
Each of the sub-shells is as per the energy levels.
The impossibility of drawing orbits for electrons
1) Heisenberg Uncertainty Principle says, you cannot know with certainty where an electron is
and where it is going next.
2) This makes it impossible to draw out an orbit or pathway in which the electrons move.

Atomic orbitals
An atomic orbital is a region of space around the nucleus where the probability of finding a
particular electron is maximum (>95%).
The sub-shells are split further into orbitals where the electrons are placed. The number of
orbital in each sub-shell depends on the sub-shells.
 s - one orbital {s}
 p - three orbitals {px, py, pz}
 d - five orbitals {dxy, dyz, dxz, dx²-y², dz²}
In the nth principal quantum shell, there are n sub-shells, n² orbitals and a maximum of 2n²
electrons.
Each orbital has a three-dimensional shape.

2
All the s orbitals are spherical and non-directional. The shaded region represents the region in
which the chance of finding the s electron is more than 95%. The size of the s orbital increases
in the order 1s < 2s < 3s < 4s.

All the p orbitals are dumb-bell shaped and directional. p orbitals are only available from the
second principal quantum shell and onwards. There are 3 types of p orbitals, p x, py and pz. All 3
different types of p orbitals are perpendicular to each other along the x, y and z axes. Going to a
higher energy level, the 'lobes' of the p orbital become longer.

3
Orbitals having the same energy are called degenerate orbitals. For example, p x, py and pz are
degenerate orbitals. The concept of orbitals arises from the fact that an electron has dual
nature. It behaves as a particle as well as a wave.

d orbitals

4
Electronic Configuration
Electronic configuration describes how the electrons in an atom/ion are arranged in their shells,
sub-shells and orbitals.

5
Filling in the orbitals
1) Three general rules of filling the orbitals are:
i. Aufbau Principle states that in the ground state of an atom, the electrons must
occupy the orbitals in the order of increasing energy. Each box represents an atomic
orbital.
The boxes (orbitals) can be arranged in order of increasing energy from bottom to
top.
An electron is represented by an arrow.

[Note: 4s has a slightly lower energy than 3d, therefore electrons are filled in 4s orbital first
before the 3d orbitals]
ii. Pauli's Exclusion Principle states that an orbital can only accommodate a maximum
of two electrons only. The two electrons must have opposite spins. (We imagine an
electron rotating around its own axis either in a clockwise or anticlockwise
direction.)

iii. Hund's Rule states that in a set of degenerate orbitals, electrons must occupy the
orbital singly first before pairing. The reason is because, two electrons occupying the
same orbital will experience repulsion.

6
Electronic configuration of the elements (up to Z = 38)

7
The odd ones (K, Sc, Cr and Cu):
i. For potassium, 4s is filled before 3d because 4s has a lower energy level than 3d.
ii. For scandium (to zinc, the d-block elements), the energy level of 3d and 4s are reversed.
4s is at a higher energy level now. This is because once the 3d orbital(s) is/are filled, the
3d electrons repel the 4s electrons to a higher energy level.
iii. For chromium, the electronic configuration is [Ar]3d⁵4s¹ instead of [Ar]3d⁴4s². This is
because orbitals that are fully filled or half-filled have extra stability due to their
symmetrical charge distribution.

iv. For copper, the electronic configuration is [Ar]3d¹⁰4s¹ instead of [Ar]3d⁹4s². The reason
is the same as stated in (iii).
Electronic configuration of ions
1) In the formation of cation, the electrons are removed in the order of decreasing energy (the
reverse of filling in).
2) For the d-block elements, the electrons in 4s is removed first before 3d. This is because once
the 3d orbital is filled, the 4s electrons are repelled to a higher energy level than 3d.
For example:
Ti atom: 1s2 2s2 2p6 3s2 3p6 3d2 4s2 -> Ti2+ ion: 1s2 2s2 2p6 3s2 3p6 3d2
Cr atom: 1s2 2s2 2p6 3s2 3p6 3d5 4s1 -> Cr3+ ion: 1s2 2s2 2p6 3s2 3p6 3d3
3) In the formation of anion, the electrons are added in the same manner as filling the
electrons.

8
Orbitals and the Periodic Table

The arrangement of elements in the Periodic Table reflects the electronic structure of the
elements. The Periodic Table can be split into blocks of elements.
The elements in the Periodic Table can be divided into four blocks according to their valence
shell electronic configuration.
 The s-block elements have their valence electron(s) in the s orbital.
 The p-block elements have their valence electrons in the p orbital.
 The d-block elements have d orbitals filling.
 The f-block elements have f orbitals filling.
Question:
1. An element has the electronic configuration 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p5.
i. Which block in the Periodic Table does this element belong to?
ii. Which group does it belong to?
iii. Identify this element.
2. Which block in the Periodic Table does the element with the electronic configuration 1s 2 2s2
2p6 3s2 3p6 3d5 4s1 belong to?
Some useful facts
 The valence electrons always appear at the end of the electronic configuration (but not
necessarily the last orbital).
 The valence electrons are largely responsible for the chemical properties of an element.
 The number of valence electron will indicate the group number of that element

9
 The outermost quantum shell number will indicate the period of that element in the
Periodic Table.
Ionisation Energy
What is ionisation energy?
1) The 1st ionisation energy, ΔHi1 is the energy needed to remove one electron from each atom
in one mole of the atoms of the element in the gaseous state to form one mole of gaseous 1+
ions.
2) The general unit for ionisation energy is kJ mol⁻¹.
Ca(g) → Ca⁺(g) + e⁻ ; ΔHi1 = +590 kJ mol⁻¹
3) If a second electron is removed from the gaseous 1+ ions, it is the 2nd ionization energy,
ΔHi2.
Ca⁺(g) → Ca²⁺(g) + e⁻ ; ΔHi2 = +1150 kJ mol⁻¹
4) The 2nd ionisation energy, ΔHi2 is the energy needed to remove one electron from each
gaseous 1+ ion in one mole of the ions to form one mole of gaseous 2+ ion.
5) The continuous removal of electrons until only the nucleus is left will result in a sequence of
ionization energies called successive ionisation energies.
Question:
1. Write equations that describe:
I. The 1st ionisation energy of calcium
II. The 3rd ionisation energy of potassium
III. The 2nd ionisation energy of lithium
IV. The 5th ionisation energy of sulfur.
2. The 2nd ionisation energy of nitrogen is 2860 kJ mol –1. The 3rd ionisation energy of nitrogen
is 4590 kJ mol–1. Explain why the 3rd ionisation energy is higher.
Factors affecting the ionisation energy
1) Charge on the nucleus (Number of proton)
- The greater the number of proton in the nucleus, the greater the amount of positive charge.
- The greater the positive charge, the greater the attractive force between the nucleus and
outer electrons.
- More energy is needed to overcome the attractive force. So, the ionisation energy is higher.
- The greater the nuclear charge, the higher the ionisation energy.
2) Distance between nucleus and outer electrons (Size of atom/ion)

10
- The larger the size of the atom, the greater the distance between the nucleus and the outer
electrons.
- The greater the distance between the nucleus and the outer electrons, the weaker the
attractive force between nucleus and outer electrons.
- Furthermore, the outer electrons experience greater shielding effect by the inner electrons.
- Less energy is required to overcome the attractive force. So, the ionisation energy is lower.
- The greater the distance between nucleus and outer electrons, the lower the ionisation
energy.
3) Shielding effect by the inner electrons
- All electrons are negatively-charged, so they repel each other. Electrons in full inner shells
will repel the outer electrons and so prevent the full nuclear charge being felt by the outer
electrons. This is called shielding or screening.
- The greater the shielding effect, the weaker the attractive force between the nucleus and
outer electrons.
- Less energy is required to overcome the attractive force. So, the ionisation energy is lower.
- The greater the shielding effect, the lower the ionisation energy.
Pattern of ionisation down a Group
1) The first ionisation energy decreases down a Group.
2) This is because the atomic size increases and hence the distance between the nucleus and
outer electrons increases. The outer electrons also experience a greater shielding effect.

These two factors outweigh the increasing nuclear

charge.
The above factors causes the attractive force between nucleus and outer electrons to decrease,
less energy is required to overcome the weaker attractive force. Hence, the ionisation energy is
lower.
Pattern of ionisation energy across a Period

11
1) The general trend of ionisation energy across a Period is increasing.
2) This is because, across a Period, the number of protons in the nucleus increases by one
therefore the nuclear charge increases.
3) However, the distance between the nucleus and outer electrons decreases across a Period
and the outer electrons experience the same amount of shielding.
4) The above factors causes the attractive force between nucleus and outer electrons to
increase, more energy is required to overcome the stronger attractive force. Hence, the
ionisation energy is higher.

The drop between (Be-B) and (Mg-Al)

1) There is a slight decrease in first ionisation energy between beryllium-boron and magnesium-
aluminium.

12
2) This is because the fifth electron in boron is located in the 2p sub-shell, which is slightly
further away from the nucleus. The outer electron in boron is shielded by the 1s² as well as 2s²
electrons.
Be : 1s²2s² B : 1s²2s²2p¹
3) The decrease in first ionisation energy between magnesium and aluminium has the same
reason, except that everything is happening at the third energy level.
Mg : 1s²2s²2p⁶3s² Al : 1s²2s²2p⁶3s²3p¹
The drop between (N-O) and (P-S)
1) There is a slight decrease in first ionisation energy between nitrogen-oxygen and
phosphorus-sulphur.
2) This is because the electron being removed in oxygen is from the orbital which contains a
pair of electrons. The extra repulsion between the pair of electrons results in less energy
needed to remove the electron. This is called spin-pair repulsion.
N : 1s²2s²2px¹2py¹2pz¹ O : 1s²2s²2px²2py¹2pz¹
3) The decrease in first ionisation energy between phosphorus and sulphur has the same
reason, except that everything is happening at the third energy level.
P : 1s²2s²2p⁶3s²3px¹3py¹3pz¹ S : 1s²2s²2p⁶3s²3px²3py¹3pz¹
Interpreting the Successive ionisation energy graphs of elements
1) The following data can be obtained from successive ionisation energy:
i. Total number of electrons in an atom- is equal to the number of separate ionisation
energies possessed by the atom.
ii. Number of principal quantum shells occupied and the number of electrons in each-by
looking the big difference between two successive ionisation energies.
iii. Number of sub-shells occupied and the number of electrons in each.
2) Successive ionisation energies get larger because removing an electron from a positive ion
with increasing positive charge is going to be more difficult due to the increasing attractive
force.

13
 There is a relatively big increase in ionisation energy between the first and second electron
being removed. This first electron is very likely to be far from the nucleus and well shielded
by other electrons. The second electron being removed is from a principal quantum shell
closer to the nucleus.
 From the second to the ninth electrons removed there is only a gradual change in
successive ionisation energies. This suggests that all these eight electrons are in the same
shell.
 The big jump occurs three times, so there are four principal quantum shells occupied by this
atom.
 After the big jumps, there is a steady increase in ionisation energy, this suggests that the
electrons being removed come from the same principal quantum shell.
 The 18th and 19th electrons have extremely high ionisation energies, when compared with
the rest of the data. This suggests that they are very close to the nucleus. There must be a
very great force of attraction between the nucleus and these electrons and there are no
inner electrons to shield them. The large increase in ionisation energy confirms that these
two electrons are in a shell closer to the nucleus than the other electrons.
 The electronic configuration for this atom can be written as 2,8,8,1 and it is potassium.
3) Two more examples:

14
Looking at the pattern in more detail

1) The electronic configuration of chlorine is 1s²2s²2p⁶3s²3px²3py²3pz¹.

2) Between the second and third ionisation energy, there is a slight increase in difference in
ionisation energy. This is because the first two electrons being removed come from the orbitals
which contain a paired electrons. The extra repulsion between the electrons result in the
ionisation energy being lower.
3) There is also a slight increase in difference in ionisation energy between the fifth and sixth
electron being removed. This is because the sixth electron being removed comes from the 3s
sub-shell, which is slightly closer to the nucleus.

15
4) The drastic increase in ionisation energy between the seventh and eighth electrons suggests
that the eighth electron comes from a principal quantum shell closer to the nucleus.

16