Learning objectives

o Understand the terms:

 shells, sub-shells and orbitals
 principal quantum number (n)
 ground state, limited to electronic configuration
o Describe the number of orbitals making up s, p and d sub-shells, and the number of
electrons that can fill s, p and d sub-shells
o Describe the order of increasing energy of the sub-shells within the first three shells and
the 4s and 4p sub-shells
o Describe the electronic configurations to include the number of electrons in each shell,
sub-shell and orbital
o Explain the electronic configurations in terms of energy of the electrons and inter-
electron repulsion
o Determine the electronic configuration of atoms and ions given the atomic or proton
number and charge, using either of the following conventions: e.g. for Fe:
1s22s22p63s23p63d64s2 (full electronic configuration) or [Ar] 3d64s2 (shorthand electronic
configuration)
 Learning objectives
o Understand and use the electrons in boxes notation e.g. for Fe: [Ar]
o Describe and sketch the shapes of s and p orbitals
o Describe a free radical as a species with one or more unpaired electrons
o Define and use the term first ionisation energy, IE
o Construct equations to represent first, second and subsequent ionisation energies
o Identify and explain the trends in ionisation energies across a period and down a group of
the Periodic Table
o Identify and explain the variation in successive ionisation energies of an element
o Understand that ionisation energies are due to the attraction between the nucleus and
the outer electron
o Explain the factors influencing the ionisation energies of elements in terms of nuclear
charge, atomic/ionic radius, shielding by inner shells and sub-shells and spin-pair
repulsion
o Deduce the electronic configurations of elements using successive ionisation energy data
o Deduce the position of an element in the Periodic Table using successive ionisation
energy data
 Materi

IKATAN KIMIA
 Materi
STABILITY OF NOBLE GAS CONFIGURATIONS
Noble gas
configurationn
Kulit n=1 n=2 n=3 n=4 n=5 n=6

2 He 2
Ne 2 8
2 He Ar 2 8 8
Kr 2 8 18 8
2 8 Xe 2 8 18 18 8
Rn 2 8 18 32 18 8

Ne
The electron configuration of noble gases is
10

classified as a full configuration and is the

2 8 8 most stable form of electron configuration with
a valence electron count of 8 (octet), except
for helium (He) which has 2 electrons (duplet).
18 Ar

IKATAN KIMIA
 Materi Simple electronic structure
we saw that electrons are arranged outside the nucleus in energy levels or quantum shells.
These principal energy levels or principal quantum shells (symbol n) are numbered according to how far they are
from the nucleus.
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 quantum shells further away from the nucleus have more energy and are held less tightly to the
nucleus.
The arrangement of electrons in an atom is called its electronic structure or electronic configuration.

Each principal quantum shell can hold a maximum number of

electrons:
 shell 1: up to 2 electrons
 shell 2: up to 8 electrons
 shell 3: up to 18 electrons
 shell 4: up to 32 electrons. The simple electronic structures of
lithium, neon and chlorine. The
nuclei of the atoms are not shown.

IKATAN KIMIA
 Materi

IKATAN KIMIA
 Evidence for electronic structure
By firing high-speed electrons at atoms, scientists can work out how much energy has to be supplied to form an ion by
knocking out one electron from each atom.
The energy change that accompanies this process is called the ionisation energy.

Ionisation energies are measured under standard conditions.

The general symbol for ionisation energy is IE.
Its units are kJ mol−1.
The symbol for the first ionisation energy is IE1.
Using calcium as an example: 1st ionisation energy: Ca(g) → Ca+(g) + e−
IE1 = 590 kJ mol−1
If a second electron is removed from each ion in a mole of gaseous 1+ ions, we call it the second ionisation energy, IE2.
Again, using calcium as an example: 2nd ionisation energy: Ca+(g) → Ca2+(g) + e−
IE2 = 1150 kJ mol−1
Removal of a third electron from each ion in a mole of gaseous 2+ ions is called the third ionisation energy.
Again, using calcium as an example: 3rd ionisation energy: Ca2+(g) → Ca3+(g) + e− IE3 = 4940 kJ mol−1
We can continue to remove electrons from an atom until only the nucleus is left. We call this sequence of ionisation energies
successive ionisation energies
 Factors that influence ionisation energy
o The size of the nuclear charge: as the atomic number (number of protons) increases, the positive nuclear charge in the
nucleus increases. The bigger the positive charge, the greater the attractive force between the nucleus and the electrons.
So, more energy is needed to overcome these attractive forces if an electron is to be removed.
In general, ionisation energy increases as the proton number increases.
o Distance of outer electrons from the nucleus: the force of attraction between positive and negative charges decreases
rapidly as the distance between them increases. So, electrons in shells further away from the nucleus are less attracted to
the nucleus than those closer to the nucleus.
In general, the further the outer electron shell is from the nucleus, the lower the ionisation energy.
o Shielding effect of inner electrons: as all electrons are negatively charged, they repel each other. Electrons in full inner
shells repel electrons in outer shells. Full inner shells of electrons prevent the outer electrons feeling the full nuclear
charge. This is called shielding. The greater the shielding of outer electrons by the inner electron shells, the lower the
attractive forces between the nucleus and the outer electrons.
In general, the ionisation energy is lower as the number of full electron shells between the outer electrons and
the nucleus increases.
o Spin-pair repulsion: electrons in the same atomic orbital in a sub-shell repel each other more than electrons in different
atomic orbitals. This increased repulsion makes it easier to remove an electron. So first ionisation energy is decreased
 Interpreting successive ionisation energies
o The figure shows a graph of successive ionisation energies against the number of electrons removed for sodium. A
logarithmic scale (to the base 10) is used because the values of successive ionisation energies have such a large
range. We can deduce the following about sodium from Figure.
o The first electron removed has a low first ionisation energy, when compared with
the rest of the data. It is very easily removed from the atom. It is therefore likely to
be a long way from the nucleus and well shielded by inner electron shells.
o The second electron is much more difficult to remove than the first electron.
There is a big jump in the value of the ionisation energy. This suggests that the
second electron is in a shell closer to the nucleus than the first electron. Taken
together, the 1st and 2nd ionisation energies suggest that sodium has one electron
in its outer shell.
o 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
o The 10th and 11th 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 between the 9th and 10th electrons confirms that the 10th
electron is in a shell closer to the nucleus than the 9th electron.
The arrangement of electrons in an atom of sodium can be deduced from
the values of successive ionisation energies

Sub-shells and atomic orbitals:

 The first principal quantum level, n = 1, can hold a maximum of 2 electrons in an s sub-
shell.
 The second principal quantum level, n = 2, can hold a maximum of 8 electrons: 2 electrons
in the s sub-shell and 6 electrons in the p sub-shell.
 The third principal quantum level, n = 3, can hold a maximum of 18 electrons: 2 electrons
in the s sub shell, 6 electrons in the p sub-shell and 10 electrons in the d sub-shell.
 The order of the sub-shells in terms of increasing energy does
not follow a regular pattern of s then p then d after the
element argon.
 The order of sub-shells after argon appears to overlap. The
next element after argon is potassium. Potassium’s outer 1s22s22p63s23p64s23d104p65s24d105p5………….
electron is in the 4s, not in the 3d, sub-shell.
 The first element with an electron in the 3d sub-shell is
element 21, scandium.
 Atomic orbitals
Each sub-shell contains one or more atomic orbitals.
An atomic orbital is a region of space around the nucleus of an atom that can be occupied by one or two electrons.
As each orbital can only hold a maximum of two electrons, the number of orbitals in each sub-shell must be:
s − one orbital
p − three orbitals
d − five orbitals
 Shapes of the orbitals
Each orbital has a three-dimensional shape. Within this shape there is a high probability of finding the electron or electrons
in the orbital.

An s orbital has a spherical shape.

The 2s orbital in the second principal quantum shell has the same shape
as the 1s orbital in the first quantum shell.
They are both spherical, but electrons in the 2s orbital have more energy
than electrons in the 1s orbital.

There are three 2p orbitals in the second quantum shell. Each of these
has the same shape.
The shape is like an hourglass with two ‘lobes’.
The three sets of ‘lobes’ are arranged at right angles to each other along
the x, y and z axes.
Hence the three 2p orbitals are named 2px, 2py and 2pz. The three 2p
orbitals have the same energy as each other.

The d orbitals are more complex in shape and arrangement in

space. In 1925 Louis de Broglie suggested that electrons behaved
like waves. This led to the idea of electron probability clouds. The
electron probability cloud for one type of d orbital has two
pieces: it is like a modified p orbital with a ring around the middle The shape of a dz2 orbital.
 Filling the shells and orbitals

The most stable electronic configuration of an atom is the one that

has the lowest amount of energy.
The order in which the sub-shells are filled depends on their relative
energy.
The sub-shell with the lowest energy, the 1s, is therefore filled first,
followed by those that are successively higher in energy. As we noted

The order of the sub-shells in terms of increasing energy does not

follow a regular pattern of s then p then d after argon, where the
3p sub-shell is full.

Aufbau principle: electrons first occupy those orbitals whose energy is the
lowest. This implies that the electrons enter the orbitals having higher energies
only when orbitals with lower energies have been completely filled.
 Electronic configurations
Representing electronic configurations
Here is a detailed way of writing the electronic configuration of an atom
of hydrogen, that includes information about the number of electrons in
each sub-shell.

 Helium has two electrons. Both electrons can go into the 1s orbital,
as this can hold a maximum of two electrons. So, the electronic
structure of helium is 1s2.
 Lithium has three electrons. The 1s orbital can only hold a
maximum of two electrons so the third electron must go into the
next highest sub-shell, the 2s. So, the electronic structure of lithium
is 1s2 2s1

‘noble gas core’ represents the electronic configuration of

Calcium : 1s2 2s2 2p6 3s2 3p6 4s2.
noble gas example, argon: 1s2 2s2 2p6 3s2 3p6. This method is a
may be written as : [Ar] 4s2
shorthand way of writing electronic structures of atoms with
many electrons.
However, in an exam you should be prepared to write out the
full electronic configuration.
 Electronic configuration of potassium

Potassium has the electronic configuration 1s2 2s2 2p6 3s2 3p6 4s1.
The outer electron goes into the 4s sub shell rather than the 3d sub-shell because the 4s is below the 3d in terms of its energy

Filling the 3d sub-shell

After calcium, a new sub-shell becomes occupied. The next electron goes into a 3d sub-shell rather than a 4p sub-shell.
So, scandium has the electronic configuration [Ar] 3d1 4s2.
This is because electrons occupy the orbitals with the lowest energy: the 3d sub-shell is just above the 4s sub-shell but below
the 4p sub shell.
This begins a pattern of filling the 3d sub-shell ending with zinc. Zinc has the electronic configuration [Ar] 3d 10 4s2.

Chromium and copper

The electronic configurations of chromium and copper do not follow the
expected pattern.
Chromium has the electronic configuration [Ar] 3d5 4s1 (rather than the
expected [Ar] 3d4 4s2).
Copper has the electronic configuration [Ar] 3d10 4s1 (rather than the
Hund's rule, atoms with half-
expected [Ar] 3d9 4s2).
filled or completely-filled
This is because the 3d54s1 and 3d104s1 electron arrangements are more
orbitals are comparably more
energetically stable. You will have to learn that these two elements are
stable
exceptions to the pattern
The electrons then add to the 4p sub-shell because this is the next highest energy level above the 3d.
 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.
 Elements in Groups 1 and 2 have outer electrons in an s sub-shell. These are therefore together called the s-
block.

 Elements in Groups 13 to 18 (apart from He) have outer electrons in a p sub-shell. These are therefore
together called the p-block.
 Elements that add electrons to the d sub-shells are called the d-block elements. Most of these are transition
elements.
 Filling the orbitals

A useful way of representing electronic configurations is a diagram that places electrons in boxes.
 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.

 The direction of the arrow represents the ‘spin’ of the electron. (We imagine an
electron rotating around its own axis either in a clockwise or anticlockwise
direction.) The electronic configuration of
 When there are two electrons in an orbital, the ‘spins’ of the electrons are boron in box form.
opposite, so the two arrows in this box point in opposite directions.

Electrons in the same region of space repel each other because they have the same charge. This is called spin-pair
repulsion.
Wherever possible, electrons will occupy separate orbitals in the same sub-shell to minimise this repulsion, so these
electrons have their ‘spin’ in the same direction.
Electrons are only paired when there are no more empty orbitals available within a sub-shell. The spins are then
opposite to minimise repulsion
 Free radicals

A free radical is a species with one or more unpaired electrons.

An example of a free radical is an isolated chlorine atom, which has the electronic configuration 1s 22s22p63s23p5.
In the 3p orbitals, two of the orbitals have paired electrons and the remaining orbital has an unpaired electron.
The unpaired electron in a free radical is shown as a dot ·, e.g. Cl·.
Groups of atoms can also be free radicals. For example, the H3C· radical has a carbon atom with an unpaired electron.

When adding electrons to a particular sub-shell, the electrons

are only paired when no more empty orbitals are available.
 Electronic configuration of ions

Positive ions are formed when electrons are removed from atoms.
The sodium ion, Na+ (proton number = 11), has 10 electrons so its electronic configuration is 1s 2 2s2 2p6.
Note that this is the same as the electronic configuration of neon, the element with 10 electrons in each atom.
Negative ions are formed when atoms gain electrons.
The sulfide ion, S2− (proton number = 16), has 18 electrons. Its electronic configuration is 1s 2 2s2 2p6 3s2 3p6, which is
the same as argon, the element with 18 electrons in each atom.
Note that, in general, electrons in the outer sub-shell are removed when metal ions form their positive ions.
However, the d-block elements behave slightly differently.
Reading across the Periodic Table from potassium to zinc, the 4s sub-shell fills before the 3d sub-shell.
But when atoms of a d-block element lose electrons to form ions, the 4s electrons are lost first.
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