4.

INTRODUCTION TO PERIODICITY

Question/key idea Notes

Introduction

The study of the elements and their compounds would involve a chaotic collection of unconnected data if
we did not have some means of organising it. Fortunately, if the elements are placed in order of atomic
number, we find that many of the properties change in a periodic fashion. We often find steady trends in a
sequence of elements, and at regular intervals elements with similar properties occur. Properties which vary
periodically include physical ones like atomic size, melting points, electrical conductivities, ionisation energy,
and electronic configuration, and chemical ones like valencies, acidity of oxides, and reaction of chlorides
with water. The first satisfactory version of a Periodic Table was put forward by Mendeléev, based on the
observed properties. The underlying reason for these variations is the electronic structure of the element,
and the modern form of the Periodic Table emphasises this by its layout. The elements are placed in order
of increasing atomic number.

When the elements are arranged in this manner, they fall into patterns:

A Group (vertical column) is a collection of elements with similar outer electronic configurations which
causes them to have similar physical and chemical properties.
A Period (horizontal row) contains all the elements with the same outer shell e.g. for all elements in Period
3, the third shell is the outer one. Across each period there is a trend (steady change) in their chemical and
physical properties, and this is repeated across the next period. Periodicity is the name given to this periodic
pattern across the rows.

1
 Question/key idea Notes
Periodicity of physical properties of Period 2 elements (Li to Ne)

NB – atomic radius is given as estimated covalent radius.

Li Be B C N O F Ne

electron config. 1s2 2s1 1s2 2s2 1s2 2s2 2p1 1s2 2s2 2p2 1s2 2s2 2p3 1s2 2s2 2p4 1s2 2s2 2p5 1s2 2s2 2p6

atomic radius /
0.123 0.089 0.080 0.077 0.074 0.074 0.072 -
nm

melting point / K 453 1553 2573 63 55 53 24

3730
(sub)
boiling point / K 1603 2750 4203 77 90 85 27

giant giant simple simple simple

structure metallic metallic atomic
covalent covalent covalent covalent covalent

first I.E / kJ mol-1 519 900 799 1090 1400 1310 1680 2080

2
 Question/key idea Notes
Periodicity of physical properties of Period 3 elements (Na to Ar)

Na Mg Al Si P (as P 4 ) S Cl Ar

electron config. [Ne] 3s1 [Ne] 3s2 [Ne] 3s2 3p1 [Ne] 3s2 3p2 [Ne] 3s2 3p3 [Ne] 3s2 3p4 [Ne] 3s2 3p5 [Ne] 3s2 3p6

atomic radius /
0.157 0.140 0.126 0.117 0.110 0.104 0.099 -
nm
melting point / K 371 923 933 1683 317 392 172 84

boiling point / K 1163 1390 2720 2630 553 718 239 87

giant simple simple simple
structure metal metal metal atomic
covalent covalent covalent covalent

first I.E / kJ mol-1 500 740 580 790 1010 1000 1260 1520

Below we look at specific trends, using Period 3 as an example. Note that all the principles should be able
to be applied to Period 2 also.

Ionisation energies: See detailed discussion of the periodic trends in ionisation energy in the ATOMIC
STRUCTURE topic notes.

3
 Question/key idea Notes
Atomic and ionic radii:

The radius of an atom depends on whether it is bonded to another one, and on the nature of the bonding
(metallic, ionic, covalent). If one compares similar types of radius, the general trend is for atoms to get
smaller across a period. This is because the nuclear charge is increasing, and the extra electrons being added
go into the same outer shell. On the whole, electrons in the same shell do not shield one another, and so
the size contracts as the nuclear charge increases across the period. The alkali metal, in Group 1, is the
largest atom, and the halogen, in group 7, is the smallest (the noble gases have not been included in the
tables above since they do not form compounds and hence their covalent radius is difficult or impossible to
measure).

Atomic Radii Across Period 3

0.18
0.16
0.14

Atomic Radius / nm
0.12
0.1
0.08
0.06
0.04
0.02
0
Na Mg Al Si P S Cl

4
 Question/key idea Notes
Melting points:
These depend on the type of bonding, and the structures of the solids. Generally, going across a period
metallic bonding increases in strength (Na<Mg<Al) as successive atoms have more protons in the nucleus
and more outer shell electrons that can delocalise, and therefore a greater attraction between the more
highly charged metal ions and the larger delocalised ‘sea’ of electrons. This then gives way to a giant covalent
structure (Si – like diamond), and then to simple molecular (monatomic in the case of Ar) substances (P 4 ,
S 8 , Cl 2 , Ar). Values for the four simple molecules reflect the number of electrons in the molecule, due to
increased London Dispersion forces (i.e. S 8 > P 4 > Cl 2 >Ar).

Melting & Boiling Points of Period 3

3000

2500

2000
Temperature / K

1500 Melting Point / K

Boiling Point / K
1000

500

0
Na Mg Al Si P S Cl Ar

5
 Question/key idea Notes
Boiling points:
These are less dependent on crystal structure, and so give a better idea of the forces between the particles.
Again we can note the increase in metallic bonding from Na to Mg to Al; the high value for the giant molecule
Si; the remainder are simple molecular structures. For these, intermolecular forces again depend on size of
molecule due to differing number of electorns: P 4 < S 8 ; then there is a fall to Cl 2 and Ar, since they have
weaker London Dispersion forces and lower boiling points.

[Electrical conductivity: along the series Na–Mg–Al the number of outer shell electrons which can be
delocalised in metallic bonding increases, and the electrical conductivity increases accordingly. By Si,
however, the effective nuclear charge is too high to allow electron delocalisation, and Si is not a metal,
although it is a semiconductor because an electron can be torn free relatively easily. The remainder are non-
metallic insulators: their effective nuclear charges are too great to allow electrons to escape under normal
conditions.]