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Physical properties and reactions of period 3 oxides

Physical properties

Group 1 2 3 4 5 6 7
Formula of oxide Na2O MgO Al2O3 SiO2 P4O10 SO2 Cl2O
Tm (K) 1548 3125 2345 1883 573 200 253
State at 298K (s) (s) (s) (s) (s) (g) (g)
Conductivity of
+ + +
molten oxide
Structure and giant giant giant giant simple simple simple
bonding ionic ionic ionic molecular molecular molecular molecular

Typical reactions with water


Melting points of period 3
Na2O Dissolves readily, negligible heat change,
colourless alkaline solution formed. oxides

MgO Only slightly soluble in water, leaves a fine white 3500


suspension in an alkaline solution. 3000
2500
Al2O3 Insoluble in water, but it will react with both Tm 2000
acids and bases to form salts, i.e. it is an (K) 1500
amphoteric oxide. 1000
500
SiO2 Insoluble in water, but it will react with bases to 0
form salts, i.e. it is an acidic oxide. 0 2 4 6 8

P4O10 Very exothermic reaction on adding to water to group number


produce an acidic solution.

SO2 A gas which dissolves readily in water to produce a colourless acidic solution.

Explanations
1. Reactions of sodium oxide and magnesium oxide with water
Hydrated ions are formed when ionic compounds dissolve in water.
If the ionic radius is small and the charge on the ion is high, hydrolysis also occurs.
When sodium oxide and magnesium oxide dissolve in water, the small highly charged oxide ions
strongly attract water molecules, so after hydration there is hydrolysis to produce hydroxide ions:

O2(aq) + H2O(l) 2OH(aq)

2. Reactions of aluminium oxide


Aluminium oxide has properties which are intermediate between those of a metallic oxide and those
of a non-metallic oxide:

Al2O3(s) + 6H+(aq) + 3H2O(l) 2[Al(H2O)6]3+ (aq) acting as a base

Al2O3(s) + 2OH (aq) + 3H2O(l) 2[Al(OH)4] (aq) acting as an acid

Copyright 2003 Nigel Saunders N-ch5-05


[Al(H2O)6]3+ is often just written as Al3+. However, this probably only exists as such in AlF3 : in
other compounds the high charge density of the ion will cause some distortion (polarisation) of the
electron cloud of any ion in contact with it causing a degree of covalent bonding. [Al(OH)4] is the
tetrahydroxoaluminate or aluminate ion.

3. Reactions of silicon dioxide


The structure of silicon dioxide (SiO2) is an extended network of SiO4 units. Each central silicon
atom is bonded covalently to four oxygen atoms, but only has a half share in four atoms. This
structure is similar to that of diamond, and silicon dioxide is more properly known as silica.
Because it has a giant covalent structure, it is insoluble in water, and it has a melting point (1996K)
and boiling point (2503K).

However, silica does react with hydroxide: SiO2(s) + 2OH (aq) SiO2-
3 (aq) + H2O(l)

SiO2-
3 is the silicate(IV) ion. This reaction is responsible for glass stoppers getting stuck in reagent
bottles containing sodium hydroxide solution.

4. Reactions of non-metallic oxides


In these oxides, oxygen is covalently bonded.

The structure of phosphorus(V) oxide (phosphorus pentoxide) is quite complex to grasp.


Phosphorus itself adopts a tetrahedral arrangement of bonds involving 4 atoms. Phosphorus(III)
oxide (P4O6) comprises the P4 molecule with an oxygen atom bonded between each PP bond.
Phosphorus(V) oxide comprises the P4O6 molecule with an oxygen atom co-ordinated to each
phosphorus atom to give the overall formula P4O10. It reacts very vigorously with water and can be
used as a powerful dehydrating agent. Various acids depending upon the amount of water used but,
in excess water, tetraoxophosphoric(V) acid is formed:

P4O10(s) + 6H2O(l) 4H3PO4(aq)

Sulphur dioxide and sulphur trioxide consist of simple molecules. Both react with water to produce
acids:

SO2(g) + H2O(l) H2SO3(aq) dissolves readily to produce sulphuric(IV) acid

SO3(g) + H2O(l) H2SO4(aq) violent exothermic reaction to produce sulphuric(VI) acid


Oxygen is a very electronegative element and so it is able to induce a slight positive charge on the
atom to which it is attached:
- + -
O=S=O
The size of the positive charge on this atom increases with the number of oxygen atoms bonded to
it. In aqueous solution, lone pairs on the oxygen atom of the water molecule are attracted to the
positively charged centre and hydrolysis occurs. This is why SO3 is more acidic than SO2.

Dichlorine oxide, Cl2O, reacts with water to produce chloric(I) acid:

Cl2O(g) + H2O(l) 2HClO(aq)


This can decompose slowly, especially in light, to form hydrochloric acid and oxygen:

2HClO(aq) 2HCl(aq) + O2(g)

N-ch5-05 (N.S. 2003)