Physical properties and reactions of period 3 oxides

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

Typical reactions with water Na2O MgO Al2O3 Dissolves readily, negligible heat change, colourless alkaline solution formed. Only slightly soluble in water, leaves a fine white suspension in an alkaline solution. Insoluble in water, but it will react with both acids and bases to form salts, i.e. it is an amphoteric oxide. Insoluble in water, but it will react with bases to form salts, i.e. it is an acidic oxide. Very exothermic reaction on adding to water to produce an acidic solution.

Melting points of period 3 oxides

3500 3000 2500

Tm 2000 (K) 1500

1000 500 0 0 2 4 6 8

SiO2 P4O10 SO2

group number

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) Al2O3(s) + 2OH (aq) + 3H2O(l) 2[Al(OH)4] (aq) acting as a base 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- (aq) + H2O(l) 3

SiO2- is the silicate(IV) ion. This reaction is responsible for glass stoppers getting stuck in reagent 3 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) SO3(g) + H2O(l) H2SO4(aq) dissolves readily to produce sulphuric(IV) acid 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)