PERIOD THREE

SODIUM TO ARGON

Recurring patterns occur everywhere in the natural world, from the beat of the heart to the
movement of the planets. The elements sodium to argon are in period three of the Periodic Table.
They represent the most straightforward unbroken trend in properties across the Periodic Table.

VARIATIONS IN PHYSICAL PROPERTIES OF THE ELEMENTS

The graph of melting point against increasing atomic number shows a distinct overall shape.
There is a steady upward trend from sodium to silicon, followed by a sharp fall from silicon to
phosphorus, and then an overall more gradual decline from phosphorus to argon.
Sodium, magnesium and aluminium are metals and thus have structures consisting of a regular
lattice of metal ions. These metal ions are surrounded by delocalized valence electrons, which
come from the one, two and three valence electrons per atom respectively. As the strength of the
metallic bond increases, the melting point will also increase.
Silicon is a metalloid. It has a giant molecular structure similar to that of diamond. The atoms in
solid silicon are bonded together covalently to four other silicon atoms in a tetrahedral
arrangement. To melt silicon requires breaking all these covalent bonds. This needs a large
amount of energy so silicon has the highest melting point in Period three.
Phosphorus exists in several crystalline forms, the two most important of which are named
according to their colour. Red phosphorus, (Tm = 590oC) consists of chains of phosphorus atoms.
White phosphorus, (Tm = 44oC) consists of individual P4 molecules. White phosphorus is very

reactive as the bonds in the small tetrahedral molecules are strained. White phosphorus must be
stored under water as it ignites spontaneously in air above 35oC.

Sulphur exists in two forms, rhombic sulphur (Tm = 113oC) and monoclinic sulphur (Tm =
119oC). Both forms of sulphur are composed of S8 crown-shaped molecules and differ only in the
arrangement in which the molecules are packed. At temperatures slightly above the melting
point, liquid sulphur consists of separate S8 crown-shaped ring molecules. The dispersion forces
holding S8 molecules together are stronger than those of holding P4 molecules together because
there is virtually double the number of electrons. As a result, sulphur melts at a higher
temperature than phosphorus.
Chlorine in the solid form consists of covalently bonded Cl2 molecules held in a regular lattice
by dispersion forces. The melting point is low because these dispersion forces are weak. Liquid
and gases chlorine consists of separate Cl2 molecules.
Solid argon consists of separate atoms held in a regular lattice by dispersion forces. These forces
are extremely weak, thus argon has a very low melting point.

ELECTRICAL CONDUCTIVITY
Electrical conductivity increases going across the period from sodium to aluminium. It then
decreases to silicon then on to other elements in the period. Metals are good electrical
conductors. Sodium, magnesium and aluminium have delocalized electrons that are free to move
and carry an electrical charge. Going from sodium to aluminium the number of delocalized
electrons available to carry charge increases and therefore electrical conductivity increases.
Silicon is a semiconductor, that is, its electrical conductivity is intermediate between those of
metals and non-metals. At temperatures above absolute zero, thermal energy causes some of the
four valence electrons of silicon to become delocalized and move freely through the lattice.
These electrons impart some conductivity to the silicon.
The other elements, phosphorus, sulphur chlorine and argon are non-metals. They have
extremely low or negligible conductivities. The electrons in phosphorus, sulphur and chlorine are
used up in covalent bonds and are not available to carry an electric charge. Argon exists as single
atoms and so its outer electrons are not free to move.

ELECTRONEGATIVITY
Elements that tend to acquire electrons in their chemical interactions are said to be
electronegative. Electronegativity of an atom provides a numerical measure of the power of that
atom in a molecule to attract electrons. Electronegativity increases going across a period.
Moving across a period, more electrons are being put in the same energy shell, resulting in
shielding of the outer electrons by the inner electrons being negligible. The effective nuclear
charge is increasing as more protons are added to the nucleus and thus electronegativity
increases.

DENSITY
The density of a substance shows its mass per unit volume. Across a period there is a general
increase in density until a maximum is reached at Group IV. This increase in density can be
related to the increasing atomic mass and decreasing atomic radius. A maximum is reached when

the atomic radius reaches a low value and the strength of the metallic or giant covalent bonding
is at a maximum (forces of attraction between atoms increases causing them to be packed close
together). The elements to the right of the period have low densities despite having higher atomic
masses and lower atomic radii because they form simple molecular structures in which
molecules are only weakly bonded by Van der Waals forces.

ATOMIC RADIUS
Atomic radius of the elements decreases going across the period. Atomic radius is influenced by
nuclear charge of the atom and shielding effect of inner electrons. Moving across a period, the
nuclear charge increases and there is no increase in the shielding of the outer electrons from this
increased pull of the nucleus. The outer electrons are therefore more strongly attracted to the
nucleus and are tightly held. The radii of the atoms across the period therefore decreases.

REACTIONS OF THE ELEMENTS WITH OXYGEN, CHLORINE AND

WATER

REACTION WITH OXYGEN

Sodium, magnesium, aluminium phosphorus and sulphur all burn in oxygen to form an oxide.

The formulae of the oxides show a smooth increase in highest oxidation number as atomic
number increases across the period. The highest oxidation number is the same as the group
number i.e. the number of electrons in the outer shell of the atom. All the outer electrons are
involved in the bonding.
The oxides of the metals are predominantly ionic, with extent of covalence increasing from
sodium to aluminium in keeping with increase in charge density of the ions Na+, Mg2+ and Al3+.

Silicon dioxide, SiO2, also called silica is essentially covalent. It has a giant covalent structure.
The oxides of phosphorus are P4O6 and P4O10. The dispersion forces between the molecules are
sufficiently strong for both oxides to exist as solids at room temperature.

Sulphur dioxide SO2 exists as individual molecules. The dipole dipole and dispersion forces
between SO2 molecules are weak, so sulphur dioxide is a gas at room temperature. Sulphur
trioxide, SO3, is composed mainly of rings of three molecules and chains whose length is not
fixed. Below 17oC, sulphur trioxide exists as a solid held together by dispersion forces between
the rings.

The oxides of chlorine are highly reactive and unstable. Cl2O and ClO2 exist as separate
molecules. These oxides therefore have low melting points and exist as gases at room
temperature and pressure. The highest oxide of chlorine (Cl2O7) has greater dispersion forces and
exists as an oily liquid under the same conditions.

REACTIONS OF THE OXIDES

See page 15 for another table showing the properties of the oxides of Period three.
Sodium oxide is a white solid. It reacts with water to give strongly basic aqueous sodium
hydroxide with a pH of about 14.

The oxide reacts vigorously with acids to produce an aqueous solution of a salt. Example

These reactions show sodium oxide as a basic oxide.

Magnesium oxide is a white powder which is only slightly soluble in water. The aqueous
solution is only weakly basic with a pH of approximately 10.

The oxide reacts readily with acids to produce an aqueous solution of a salt. Example

These reactions indicate magnesium oxide is a basic oxide.

Aluminium oxide, Al2O3, is a white solid which is very insoluble in water. The hydrated oxide of
formula Al2O3 H2O, ( where can vary from 1 to 3), behaves as if it had the formula, Al(OH)3.
It acts as a base when it reacts with excess acid.

The hydrated oxide acts as an acid when it reacts with excess aqueous sodium hydroxide to form
a complex ion called the tetrahydroxoaluminate ion, sometimes called the aluminate ion.

Aluminium oxide therefore has the properties of both an acidic and a basic oxide.
Silica is highly insoluble in water. It reacts only with highly concentrated alkalis or at high
temperature. Example, it reacts with molten sodium hydroxide at 350oC to form sodium silicate.

Phosphorus (V) oxide P4O10 reacts with water to form aqueous phosphoric acid, which has a pH
of about 1

Anhydrous phosphoric acid exists as deliquescent colourless crystals which melt at Tm = 42oC.
Phosphorus (III) oxide P4O6 reacts with water to form aqueous phosphonic acid, H3PO3.
Sulphur dioxide SO2 is a gas with moderate solubility in water, forming an aqueous solution of
sulphurous acid, (pH = 1).

The acid cannot be isolated in the anhydrous state, as it decomposes back to the gas.
Sulphur trioxide SO3 is a solid, Tm = 17oC and Tb = 45oC, which reacts with water to form
aqueous sulphuric acid.

Sulphuric acid is a strong acid. The aqueous acid has a pH close to 0. The anhydrous acid may be
isolated as an oily liquid which boils at Tb = 338oC.
Chlorine oxides are explosive. Dichlorine oxide, Cl2O, reacts with water to give aqueous
hypochlorous acid HClO(aq). Dichlorine heptaoxide, Cl2O7, reacts with water to give aqueous
perchloric acid HClO4(aq).

REACTION WITH CHLORINE

The elements of Period three, from sodium to phosphorus react directly with chlorine to form
chlorides. The metallic chlorides form ionic chlorides while the non-metallic elements form
covalent chlorides.
Oxidation number of the chlorides increases from +1 to +5 in the sequence form sodium chloride
to phosphorus pentachloride. Phosphorus also forms phosphorus trichloride. Sulphur forms a
number of chlorides such as S2Cl2.
Sodium and magnesium chlorides are formed by heating the metal in air until it burns and then
lowering it into a vessel containing chlorine. Sodium and magnesium continue to burn in the
chlorine with the white product coating the walls of the reaction flask.

Aluminium chloride reacts readily with water, so it must be synthesized under anhydrous
conditions. A stream of dry chlorine gas is passed over heated aluminium. The aluminium
chloride product condenses as a white powder.

Aluminium chloride molecules can form dimers of formula Al2Cl6. The chlorine atoms donate
lone pairs of electrons into the valence shell of the aluminium atoms.

Silicon tetrachloride is prepared in an apparatus similar to that used for the synthesis of
aluminium chloride. However, silicon tetrachloride is a liquid at room temperature.

Heating phosphorus in excess chlorine forms the pentachloride, PCl5, while excess phosphorus
forms the trichloride, PCl3.

The pentachloride is a solid and the trichloride is a liquid at 25oC and 1 bar. The hot product
vapours must be condensed.

REACTIONS OF THE CHLORIDES WITH WATER

The chlorides of sodium and magnesium are predominantly ionic. They are white solids with
high melting points which dissolve in water to form a neutral solution. (pH = 7)

All the other chlorides of Period three have significant covalent character and react with water.
These reactions are called hydrolysis reactions.

Aluminium forms two solid chlorides, one is anhydrous (Al2Cl6) and the other hydrated
(AlCl36H2O). The anhydrous chloride reacts with water evolving hydrogen chloride gas.

The hydrated chloride consists of a complex cation [Al(H2O)6]3+ bonded ionically to three
chloride ions. The formula is therefore more accurately expressed as [Al(H2O)6]Cl3. It dissolves
in water as is typical of an ionic solid to form the ions [Al(H2O)6]3+(aq) and Cl(aq). The solution is
slightly acidic. Since the aluminium ion is relatively small and highly charged, it draws the
electron density away from the water molecules in the complex ion causing them to give up the
H+ ions.

The chlorides of silicon, phosphorus and sulphur are predominantly covalent and react with
water to form acids.