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What is periodicity?
The term periodicity describes a repeating pattern in properties of elements across periods of the periodic table. The Russian chemist Dmitry Mendeleev is credited with being the creator of the first version of the periodic table. He observed that when the elements are arranged in order of atomic mass, there are recurring patterns in certain properties. The modern periodic table can be used to analyse trends in properties such as atomic radius across periods and down groups.
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What is atomic radius?

The atomic radius of an element is difficult to precisely define because of the uncertainty over the size of the electron cloud. Several definitions are used.

One definition is half the shortest internuclear distance found in the structure of the element.
For non-metallic elements, the covalent radius is often used as the atomic radius. This is half the internuclear distance between two identical atoms in a single covalent bond.

covalent radius

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More on atomic radius

For non-bonded adjacent atoms (e.g. in a covalent crystal of a non-metallic element), the van der Waals radius is used as a value for atomic radius. This is half the shortest internuclear distance between two similar non-bonded atoms. van der Waals radius

For metallic elements, the metallic radius is often used as the atomic radius. This is half the shortest internuclear distance between two adjacent atoms in a metallic bond.
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Trends in atomic radius in period 3

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Trends in atomic radius in period 3

Atomic Element radius (nm)
Na Mg 0.190 0.145 0.118 0.111 0.098 0.088 0.079 The atomic radius of the elements across period 3 decreases. This might seem counterintuitive, because as the numbers of sub-atomic particles increase, the radius might be expected to also increase.

Al
Si P S Cl

Ar
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0.071

However, more than 99% of the atom is empty space the nucleus and electrons themselves occupy a tiny volume of the atom.

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Increase in proton number

The number of protons in the nucleus of the atoms increases across period 3.
proton number

Element

11Na 12Mg 13Al

14Si

15P

16S

17Cl

18Ar

This increase in the number of protons increases the nuclear charge of the atoms. The nucleus has stronger attraction for the electrons, pulling them in closer and so the atomic radius decreases across the period. increased nuclear charge pulls electrons closer

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What is shielding?

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Explaining atomic radius in period 3

Atomic Proton Element number radius (nm) Na Mg Al 11 12 13 0.190 0.145 0.118 Proton number increases across period 3, but shielding remains approximately constant. This causes an increase in effective nuclear charge, leading to a greater attraction between the nucleus and the outermost electrons. This pulls these electrons closer to the nucleus and results in a smaller radius.
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Si
P S

14
15 16 17 18

0.111
0.098 0.088 0.079 0.071

Cl
Ar
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Atomic radius in period 3

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Atomic radius: true or false?

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What is first ionization energy?

Ionization is a process in which atoms lose or gain electrons and become ions. The first ionization energy of an element is the energy required to remove one electron from a gaseous atom. M(g) M+(g) + eThe first ionization energy is therefore a measure of the strength of the attraction between the outermost electrons and the nucleus. The first ionization energies of the elements in periods 2 or 3 can give information about their electronic structure.
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Plot of the first ionization energies

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General trend in first ionization energy

ionization energy (kJ mol-1)

There is a general increase in the first ionization energies across period 3.

1600 1400 1200 1000 800

Across period 3, the 600 proton number 400 increases but the Na Mg Al Si P S Cl Ar amount of shielding element does not change significantly. The effective nuclear charge therefore increases.

The greater attraction between the nucleus and the outermost electrons means that more energy is required to remove an electron.
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Trend in first ionization energy: exceptions

There are two exceptions to the general trend in first ionization energy: both aluminium and sulfur have lower ionization energies than might be expected. 1600 1400 1200 1000 800 600 400 Na Mg Al

ionization energy (kJ mol-1)

lower ionization energies than expected Si P S Cl Ar

element
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First ionization energy of Al vs. Mg

The first ionization energy of aluminium is less than that of magnesium, even though aluminium has a higher nuclear charge. The electron removed when aluminium is ionized is in a 3p sub-level, which is higher in energy than the 3s electron removed when magnesium is ionized. Removing an electron from a higher energy orbital requires less energy.

magnesium

aluminium

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First ionization energy of S vs. P

The first ionization energy of sulfur is less than that of phosphorus, even though sulfur has a higher nuclear charge. The highest energy electron in both phosphorus and sulfur is in the 3p sub-level. However, in sulfur this electron is paired, while in phosphorus each 3p orbital is singly occupied. Mutual repulsion between paired electrons means less energy is required to remove one of them.

phosphorus

sulfur

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Ionization energy in period 3

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Ionization energy in period 3

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Plot of the melting and boiling points

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Na, Mg and Al: melting and boiling points

The melting and boiling points increase for the three metallic elements from sodium to aluminium. 3000 temperature (K)

2500
2000 1500 1000 500 melting point Mg element Al boiling point

0 Na

This is because the strength of the metallic bonds increases. More energy is needed to break the stronger metallic bonds, so melting and boiling points are higher.

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Na, Mg and Al: metallic bond strength

The increase in metallic bond strength from sodium to aluminium is due to two factors:

1. Charge density. This is the ratio of an ions charge to its size. Na+ ions are large with a small charge, so have a low charge density. Al3+ ions are smaller with a larger charge, and so have a higher charge density. They are therefore more strongly attracted to the delocalized electrons.
2. Number of free electrons. Sodium has one free electron per metal ion, whereas aluminium has three. This leads to more attractions that must be broken in aluminium.
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Silicon
Silicon has a macromolecular structure similar to that of diamond. Each silicon atom is bonded to four neighbouring silicon atoms by strong covalent bonds. These must be broken in order for silicon to melt. This requires a lot of energy, so silicon's melting and boiling points are high.

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Period 3 non-metals
The melting and boiling points of phosphorus, sulfur and chlorine are much lower than those of silicon. This is because they have a simple molecular structure with weak van der Waals forces holding the molecules together.
temperature (K) 3500 3000 2500 2000 1500 1000 500 0 Na

Mg

Al

Si P element

Cl

Ar

Breaking these forces of attraction requires much less energy than breaking covalent bonds.
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Period 3 non-metals: structure

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Melting points in period 3

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Melting points in period 3

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Glossary

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Whats the keyword?

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Multiple-choice quiz

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Physical Properties of Group 2 Metals

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Physical properties
The arrangement of the periodic table is such that trends can be analysed both across a period and down a group.

Group 2 of the periodic table is shown here. Trends that can be analysed down the group include atomic radius, first ionization energy and melting point.

Elements in the same group also undergo similar chemical reactions.

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Trend in atomic radius

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Explaining the trend in atomic radius

The atomic radius of the elements increases down Element group 2 from beryllium to barium. The number of protons increases down the group; however, so does the number of shielding electrons. Effective nuclear charge therefore remains approximately constant. beryllium magnesium calcium strontium barium Atomic radius (nm) 0.112 0.145 0.194 0.219 0.253

The increase in radius is due to higher principle energy levels being filled, whose orbitals are located further from the nucleus.
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Trend in first ionization energy

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First ionization energies in group 2

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Trend in melting points

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Explaining the trend in melting points

The melting points of the elements decrease down group 2, with the exception of magnesium to calcium. A metals melting point depends on the strength of its metallic bonds. This decreases down the group because the atomic radius increases, resulting in a weaker attraction between the nucleus and delocalized electrons. Element beryllium Melting point (K) 1560

magnesium
calcium strontium

923
1115 1050

barium

1000

The melting point of magnesium is lower than expected due to variation in how its atoms pack in the metallic crystal.
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Physical properties summary

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First ionization energy of group 2 metals

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The Halogens

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What are the properties of the halogens?

All the halogens are:

non-metals and so do not conduct electricity

brittle and crumbly when solid

poisonous and smelly.

They become darker in colour down the group: is pale yellow

is green-yellow
is dark orange

is dark grey.

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Predicting properties
The melting and boiling points of the halogens increase down the group as the molecules become bigger. Halogen Relative size

Melting point (C)

-220 -101

Boiling State (room point (C) temperature)

-118 -34 gas gas

-7

59

liquid

114

184

solid

What is the state of each halogen at room temperature?

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Electron structure and reactivity

The reactivity of alkali metals decreases going down the group. What is the reason for this? The atoms of each element get larger going down the group. F

Cl

The further the outer shell is from the positive attraction of the nucleus, the harder it is to attract another electron to complete the outer shell.
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decrease in reactivity

This means that the outer shell gets further away from the nucleus and is shielded by more electron shells.

The Alkali Metals (Group 1)

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Where are the alkali metals?

The elements in group 1, on the left of the periodic table, are called the alkali metals. lithium sodium potassium rubidium caesium Li Na

K
Rb

Cs
Fr

francium

These metals are all very reactive and are rarely found in nature as pure elements.

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Melting and boiling point

The melting and boiling points of alkali metals decrease down the group.

Element lithium

Melting point (C) 181

Boiling point (C) 1342 883 760 686 671

sodium
potassium rubidium caesium

98
64 39 28

This is because, as the atoms get larger, the attraction between the positive metal ions and the delocalized sea of electrons gets weaker and so the metals become easier to melt and boil.

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How does electron structure affect reactivity?

The reactivity of alkali metals increases going down the group. Why is this?

increase in reactivity

Li

The atoms of each element get larger going down the group.

Na

This means that the outer shell electron gets further away from the nucleus. The further an electron is from the positive nucleus, the easier it can be lost in reactions.

This is why the reactivity of the alkali metals increases going down group 1.
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