Cambridge AS & A Level Chemistry 9701

Notes
2 Electrons in Atoms
Cambridge AS & A Level Chemistry

Simple Electronic Structure

Simple electronic structure

• 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 further electrons in quantum shells from the nucleus is, the higher the energy
and less tightly detained to the nucleus.
• The arrangement of electrons in an atom is electronic structure or electronic
configuration.

lithium neon chlorine

2,1 2,8 2, 8, 7

Maximum number of electrons each principal quantum shell can hold:

Shell 1 up to 2 electrons Shell 2 up to 8 electrons

Shell 3 up to 18 electrons Shell 4 up to 32 electrons

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Evidence for Electronic Structure

Ionisation energy, IE

• Ionisation energy (IE) is the amount of energy needed to form an ion by removing
out one electron from each atom, measured under standard conditions with the
unit kJ mol–1.
• The first ionisation energy of an element is the energy needed to remove one
electron from each atom in one mole of atoms of the element in the gaseous state
to form one mole of gaseous 1+ ions.
• If a second electron is removed from each ion in a mole of gaseous 1+ ions, it is
called the second ionisation energy.
• Removal of a third electron from each ion in a mole of gaseous 2+ ions is called
the third ionisation energy.
• The removal can go on until only the nucleus is left. This sequence is called
successive ionisation energies.

Successive ionisation energies for the first 11 elements in the Periodic Table (kJ mol –1)

Element Electrons removed

1 2 3 4 5 6 7 8 9 10 11
H 1310
He 2370 5250
Li 519 7300 11800
Be 900 1760 14850 21000
B 799 2420 3660 25000 32800
C 1090 2350 4620 6220 37800 47300
N 1400 2860 4580 7480 9450 53300 64400
O 1310 3390 5320 7450 11000 13300 71300 8410
F 1680 3370 6040 8410 1100 15200 17900 92000 106000
Ne 2080 3950 6150 9290 12200 15200 20000 23000 117000 131400
Na 494 4560 6040 9540 13400 16600 20100 25500 28900 141000 158700

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Evidence for Electronic Structure

Factors that influence ionisation energy

1. The size of the nuclear charge

• The higher the proton number is, the greater the attractive force between
the nucleus and the electrons, and the higher the ionization energy is.
2. Distance of outer electrons from the nucleus
• The further the outer electron shell is from the nucleus, the lower the
ionisation energy.
3. Shielding effect of inner electrons
• Shielding is the attraction between an electron and the nucleus in any atom
with more than one electron.
• The greater the shielding of outer electrons by the inner electron shells, the
lower the attractive forces between the nucleus and the outer electrons.
• The ionisation energy is lower as the number of full electron shells between
the outer electrons and the nucleus increases.
4. Spin-pair repulsion
• Electrons in the same atomic orbital in a sub-shell repel each other more
than electrons in different atomic orbitals.
• The higher increased repulsion is, the easier it is to remove an electron and
first ionisation energy is decreased.

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Evidence for Electronic Structure

Interpreting successive ionisation energies

Deducing from the graph

• The first electron removed has a low first ionisation

energy so it is very easily removed from the atom.
• It is likely to be a long way from the nucleus and well
shielded by inner electron shells.
• There is a big jump in the value of the ionisation energy
started on the second electron until the ninth electron,
which suggests that all eight electrons are in the same
shell.
• The tenth and eleventh electrons have extremely high
ionisation energies, which suggests that they are very
close to the nucleus.
• The large increase in ionisation energy between the
ninth and tenth electrons confirms that the tenth electron
is in a shell closer to the nucleus than the ninth electron.

From the deduction, the arrangement of the electrons is:

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Sub-shells and Atomic Orbitals

Quantum sub-shells

• The principal quantum shells, apart from the first, split into sub-shells (sub-levels).
• Each principal quantum shell contains a different number of sub-shells
(distinguished by the letters s, p or d).
• There are also f subshells for elements with more than 57 electrons.
• The energy of the electrons in the sub-shells increases in the order s < p < d, with
the maximum number of electrons that are allowed in each sub-shell is:
s = 2 electrons, p = 6 electrons, d = 10 electrons.

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Subshells and Atomic Orbitals

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.
• Each sub-shell contains one or more atomic orbitals.
• Each orbital can only hold a maximum of two electrons, so the number of orbitals
in each subshell must be:
s = one orbital, p = three orbitals, d = five orbitals

Shape of s orbitals Shape of s orbitals

Spherical shape Double lobes

Filling the shells and orbitals: the order of

filling the sub-shells

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Electronic Configuration

Representing electronic configurations

Electronic configuration for the first 18 elements in

the Periodic Table

Electronic configuration of potassium

Potassium has the electronic structure:

1s2 2s2 2p6 3s2 3p6 4s1.
The outer electron goes into the 4s subshell
rather than the 3d subshell because the
energy of 4s is below 3d.

Chromium and copper

The electronic configurations of chromium

and copper do not follow the expected
pattern.

• Chromium has the electronic

configuration [Ar] 3d5 4s1 (instead of [Ar]
3d4 4s2).
• Copper has the electronic configuration
[Ar] 3d10 4s1 (instead of [Ar] 3d9 4s2).
This is because the electron arrangements
are more energetically stable.

Gallium to krypton

The electrons are added to the 4p subshell

because this is the next highest energy level
above the 3d.

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Electronic Configuration

Orbitals and the Periodic Table

• Elements in Groups 1 and 2 have outer electrons in an s subshell.

• Elements in Groups 3 to 18 (apart from He) have outer electrons in a p subshell.
• Elements that add electrons to the d subshells 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 arrow represents an electron.
• The direction of the arrow represents the ‘spin’ of the electron.
• When there are two electrons in an orbital, the ‘spins’ of the electrons are opposite, so the two
arrows in this box point in opposite directions.
• When adding electrons to a particular sub-shell, the electrons are only paired when no more
empty orbitals are available.

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Electronic Configuration

Electronic configuration of ions

• Positive ions are formed when electrons are removed from atoms.
• Negative ions are formed when atoms gain electrons.
• Electrons in the outer subshell are removed when metal ions form their positive
ions.
• However, the d-block elements behave slightly differently, as in when atoms of a
d-block element lose electrons to form ions, the 4s electrons are lost first.

Worked example

Use 1s2 notation to deduce the electronic configuration of an Fe3+ ion.

Step 1 Deduce the number of electrons in an iron atom (= number of protons shown in the Periodic
Table for iron) = 26
Step 2 Deduce the electronic configuration of an iron atom by adding the electrons to the orbitals in
order. Remember to fill the 4s before the 3d. = 1s 2 2s2 2p6 3s2 3p6 4s2 3d6
Step 3 For a 3+ ion, remove three electrons.

• the 2 outer s-electrons are removed first: 1s2 2s2 2p6 3s2 3p6 4s2 3d6 → 1s2 2s2 2p6 3s2 3p6 3d6
• outer d-electron is then removed: 1s2 2s2 2p6 3s2 3p6 3d6 → 1s2 2s2 2p6 3s2 3p6 3d5

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Periodic Patterns of Atomic and Ionic Radii

Patterns of atomic and ionic radius

Atomic radius Ionic radius
Down the group: Down the group:
• Atomic radii increases. • Ionic radii increases.
• Each successive element has one • Number of electrons lost or gained by each
more shell of electrons which is element in the group is generally the same.
further from the nucleus. • Each successive element has one more shell
• Nuclear charge increases. of electrons which is further from the nucleus.
• Inner shell electrons shielding the • Inner shell electrons shielding the outer shell
outer shell electrons effect electrons effect increases.
increases. Across the period:
Across the period: • Ionic radii decreases.
• Atomic radii decreases. • Number of protons and the nuclear charge
• Number of protons and the nuclear increases.
charge increases. • The shielding is approximately the same.
• Number of electrons increases by • Positively charged ions are smaller than their
one but the extra electron added original atoms because they have lost their
goes into the same (outer) energy outer shell electrons.
level. • Negatively charged ions in Groups 15 to 18
• The shielding does not change are larger than their original atoms because
significantly. each atom gained one or more extra
• The greater attractive force of the electrons into their outer energy level.
increased nuclear charge on the • From Group 15 to Group 18, the ionic radius
outer shell electrons pulls them decreases due to the normal charge on the
closer to the nucleus. ions decreasing.

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Patterns in Ionisation Energies in the Periodic Table

Patterns across a period

• There is a general increase in IE across a period (applies to Period 1 (hydrogen

and helium), Period 2 (lithium to neon), and to other periods).
• Across a period, the nuclear charge increases. Since the electron removed comes
from the same shell, the force of attraction between the positive nucleus and the
outer negative electrons increases across the period. The distance between the
nucleus and the outer electron remains reasonably constant, and the shielding by
inner shells remains reasonably constant.
• There is a rapid decrease in ionisation energy between the last element in one
period and the first element in the next period. The force of attraction between the
positive nucleus and the outer negative electrons decreases because the distance
between the nucleus and the outer electron increases, the shielding by inner shells
increases, and these two factors outweigh the increased nuclear charge.

Patterns down a group

The first ionisation energy decreases as you go down a group in the Periodic Table.
For example, in Group 1 the values of IE are:
As it goes down the group, the outer electron
Li = 519 kJ mol–1
removed is from the same type of orbital but
Na = 494 kJ mol–1
from a successively higher principal quantum
K = 418 kJ mol–1
level: 2s from lithium, 3s for sodium and 4s
Rb = 403 kJ mol–1
for potassium.
Although the nuclear charge is increasing down the group, there is less attraction between
the outer electron and the nucleus because:
1) The distance between the nucleus and the outer electron increases
2) The shielding by complete inner shells increases
3) These two factors outweigh the increased nuclear charge.

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