Periodic Trends and Patterns

The Periodic Table

Newlands was one of the first chemists to describe a repeating pattern in physical and
chemical properties when the elements were placed in order of atomic weight his Law of
Octaves, although it did not work for all elements, was the first periodic law.
Mendeleevs organization of the periodic table into atomic weight order, with elements
having matching properties being placed in the same column, required him to leave gaps
where the properties did not match. These he attributed to elements that had not yet been
discovered, and he went on use his table to successfully predict the properties of these
undiscovered elements based on the properties of known elements in the same Group.
The modern periodic table is arranged in order of increasing atomic number (proton
number), with a new Period (row) started every time electrons occupy a new shell. The
consequence of this is that elements in each Group (column) have the same number of
outer shell electrons and therefore similar physical and chemical properties.
This also means that there are repeating trends and patterns in physical and chemical
properties from one period to the next, which we refer to as periodicity. Using Period 3 as
an example, we can start to examine some periodic properties that show the same patterns
and trends across other groups.
i) Electron arrangement
Electron arrangements in Period 3
Na

Mg

Al

Si

Cl

Ar

[Ne] 3s1

[Ne] 3s2

[Ne] 3s2 3p1

[Ne] 3s2 3p2

[Ne] 3s2 3p3

[Ne] 3s2 3p4

[Ne] 3s2 3p5

[Ne] 3s2 3p6

Electron arrangements in Period 2

Li

Be

Ne

[He] 2s1

[He] 2s2

[He] 2s2 2p1

[He] 2s2 2p2

[He] 2s2 2p3

[He] 2s2 2p4

[He] 2s2 2p5

[He] 2s2 2p6

Across Period 3 we see an increasing number of electrons in the n=3 shell, with the 3s
subshell being filled first, followed by the 3p subshell. Exactly the same pattern is seen
across Period 2 with the filling of the 2s and 2p subshells
Period 4 shows the same periodic trend too, although the pattern is there interrupted by the
filling of the 3d subshell after 4s is filled.
ii) Bonding and Structure
Period 3

Na

Mg

Al

Si

Cl

Ar

Structure

Giant
metallic

Giant
metallic

Giant
metallic

Giant
covalent

metallic

metallic

metallic

covalent

Simple
molecular
S8
covalent

Simple
molecular
Cl2
covalent

Single
atoms

Bonding in
element*

Simple
molecular
P4
covalent

N/A

*bonding becomes increasingly covalent in character across the period

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Bonding in the Period 3 elements and their compounds becomes increasingly covalent in
character across the period. Aluminium shows ionic bonding in some compounds and polar
covalent bonding in others. This is because Aluminium is more electronegative than Group
1 or 2 metals, so there is less of a difference in electronegativity between aluminium and
the non-metals it bonds with. The same trend towards increasingly covalent bonding
character is seen in the other Periods.
The pattern in types of structure across Period 3 is also seen in the other groups, with the
first elements in the period being giant metallic, then giant covalent, and the remaining
elements having simple molecular structure.
iii) Melting point and boiling point
The patterns in bonding and structure form the basis for the patterns in melting and boiling
points across Period 3, which are also repeated in other Periods.
Period 3

Na

Mg

Al

Si

Cl

Ar

mp C
bp C

98
883

649
1107

660
2467

1410
2355

44
281

113
445

-101
-35

-189
-186

Melting points relate to the type of structure. The more energy needed to break down the
structure so that the particles can move around, the higher the melting point will be.
Elements with a giant structure (giant metallic lattice Na, Mg and Al, and the giant covalent
lattice of Si) all require a lot of energy to break the strong bonds holding the atoms/ions
together in the lattice, so the melting points are high.
From sodium to aluminium the melting and boiling points increase because:
the ions have greater charge and so are more strongly attracted to the delocalized
electrons [Na+, Mg2+, Al3+]
there are an increasing number of delocalized electrons for the metal ions to be
attracted to [Na Na+ + e-, Mg Mg2+ + 2e-, Al Al3+ + 3e-]
so more energy is need to overcome these strong electrostatic attractions in order to
break the metallic bonds
Elements with simple molecular structures have only weak intermolecular forces holding
the molecules together. To overcome these so that the molecules can move around
requires little energy, so the melting points are low. We DONT have to break the strong
covalent bonds holding atoms together inside each molecule. Trends in boiling points
follow the same pattern as the melting points, at a higher temperature.
For P4, S8 and Cl2 and Ar the size of the intermolecular forces (and therefore how high the
melting and boiling points are) depends on the number of electrons in the molecule. The
more electrons there are, the stronger the intermolecular forces (London forces we'll meet
these in more detail later).
The trend in melting points is therefore S8 > P4 > Cl2 > Ar since the numbers of electrons in
the molecules are 128, 60, 34, 18 respectively.
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iv) Electrical conductivity

Period 3: Na
Bonding
Conductivity

Mg

Al

metallic metallic
metallic
Good
Good
Good
and getting better

Si

covalent
covalent
covalent
Poor
Poor
Poor
and getting worse

Cl

Ar

covalent
Poor

N/A
Poor

Electrical conductivity is also related to the type of bonding. Na, Mg and Al have metallic
bonding. They are good conductors because they possess mobile delocalised electrons
which can carry the charge. Al is a better conductor (of both heat and electricity) than Na
because it donates 3 outer shell electrons rather than 1 into the sea of delocalised
electrons.
The remaining elements in the period have covalent bonding, and do not contain any
mobile delocalised electrons, so they are poor conductors. They get increasingly poor
because an electron has to be removed from the outer shell in order for conduction to take
place, and the first ionization energies increases across the period.
v) Atomic radius
The electron cloud surrounding an atom does not have a specific end, so it is not possible
to measure to the edge of the electron cloud to measure the atomic radius. One solution is
measure the distance between bonded atoms, taking half the bond length as the atomic
radius. This is why we cant measure it for noble gases.
Period 3
Atomic
radius (nm)

Na
0.190

Mg
0.160

Al
0.130

Si
0.118

P
0.110

S
0.102

Cl
0.099

Ar
N/A

Note: 1nm = 1 x 10-9m

The atomic radius decreases across each period. Across the period there are the same
number of filled inner shells and hence the same shielding, but an increasing number of
protons in the nucleus and hence greater nuclear charge. This leads to increasing
attraction between the nucleus and the outer shell electrons across the period, and as a
result the outer shell electrons are pulled closer to the nucleus, decreasing the atomic
radius.
vi) First ionisation energies
Consider the first ionisation energies of
the first 40 elements:
There are clear patterns in the
ionisation energies across one period
compare to other periods compare
Period 2 and Period 3, for example,
and note the same pattern in Period 4
if the d-block elements are ignored.

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There is a generally increasing trend in Hi1 across Period 3, although we also see a small
dip after Mg and again after P, so we need to be able to explain why ionisation of Al and S
requires a little less energy than might be expected.
Across a period:
Across a period the electron being removed in first ionisation comes from the same shell,
and the outer shell electrons experience the same shielding from filled inner shells, but the
number of protons increases and hence the nuclear attraction towards the electron being
removed increases. As a result it requires an increasing amount of energy to remove an
outer shell electron across the group.
If we consider the outer shell electron arrangement in more detail:
Na

Mg

Al

Si

Cl

Ar

[Ne] 3s1

[Ne] 3s2

[Ne] 3s2 3p1

[Ne] 3s2 3p2

[Ne] 3s2 3p3

[Ne] 3s2 3p4

[Ne] 3s2 3p5

[Ne] 3s2 3p6

In Na and Mg, first ionisation involves removal of an electron from the 3s subshell. For Al
through to Ar, first ionisation involves removal of an electron from the 3p subshell. The 3p
subshell is higher in energy than the 3s, with the electrons on average a little further from
the nucleus and hence less strongly attracted. As a result the removal of electrons from 3p
takes a little less energy than from 3s, and we see a small downwards step in first
ionisation energies between Mg and Al. This is experimental evidence supporting the
current subshell model of atomic structure.
In Al, Si and P the three 3p orbitals are all singly-filled. From S to Ar the 3p orbitals are
progressively filled with two electrons. Electrons occupying the same orbital experience
mutual repulsion even though the opposite spins minimize this, and hence it takes a little
less energy to remove an electron from a doubly-filled orbital than a singly filled orbital in
the same subshell. As a result there is a small downwards step in the first ionisation
energies between P and S. This is experimental evidence supporting the way orbitals in the
subshells are filled in the current model of atomic structure.
Comparing periods: As we finish one period and start the next, the same overall pattern of
Hi1 is seen, but each successive period repeats at lower Hi1 values. Each time we finish
a period and start the next, the nuclear charge continues to increase as the atomic number
increases, however this increasing attraction towards the electron being removed is
outweighed by the fact that when we start a new period we start a new principle quantum
shell, so the ionised electron is further from the nucleus, and we have one more filled inner
shell shielding the ionised electron from the nuclear charge. For these reasons the
attraction between the outer shell electrons and the nucleus is decreased and less energy
is required for first ionisation.
Trend in first ionisation energies down a Group
Although it is not a periodic property, we also need to be able to explain the decreasing
trend in first ionisation energies down a group.

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Down a group, the electron being removed during ionisation comes from a shell
progressively further out from the nucleus. The electron is also shielded from the nuclear
charge by progressively more filled inner shells, and both of these factors cause a
decreasing attraction between the outer shell electrons and the nucleus, outweighing the
effect of the increased nuclear charge as the number of protons increases down the group.
With the decreasing attraction, less energy is needed to remove an outer shell electron,
and hence the first ionisation energies decrease down a Group.
Check your understanding:
1.
Why does Ne have a higher first ionization energy than Ar ?
2.
Why do first ionisiation energies increase from Al to Si to P ?
3.
Why is the first ionization energy of Na much less than that of Ne ?

Answers
1.
The electron removed on ionization of Ne is from the n=2 principle quantum shell, whereas
in Ar the electron is removed from the n=3 shell. The n=2 shell is nearer to the nucleus and
therefore the ionized electron in Ne experiences a stronger attraction to the protons in the
nucleus, which requires more energy to overcome. There is also less shielding (only the
n=1 shell shields this electron from the nucleus, whereas for Ar the n=2 shell also shields
the ionized electron from the nuclear charge). These factors outweight the increasing
nuclear charge going from Ne to Ar.
2.
In all three of these atoms the ionized electron is being removed from the n=3 principle
quantum shell, so the shielding from n=2 and n=1 shells is the same in each of these
atoms. However, going from Al to Si to P there is one more proton in the nucleus each time
so the attraction of the nucleus is stronger, and requires more energy to overcome.
3.
The electron removed on ionization of Na is from the n=3 principle quantum shell, whereas
in Ne the electron is removed from the n=2 shell. The n=3 shell is further from the nucleus
and therefore the ionized electron in Na experiences a weaker attraction from the protons
in the nucleus, which requires less energy to overcome. There are also two filled shells
shielding the ionized electron in Na whereas only one filled inner shell shields the ionized
electron in Ne. These factors outweight the increasing nuclear charge going from Ne to Na.

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