Topic 14 Metal Ions in Solution Revision Notes 1) Metal-aqua ions

When metal compounds dissolve in water, metal-aqua ions are formed 2+ metal-aqua ions include: [Fe(H2O)6]2+, [Co(H2O)6]2+ and [Cu(H2O)6]2+ 3+ metal-aqua ions include: [Al(H2O)6]3+, [V(H2O)6]3+, [Cr(H2O)6]3+ and [Fe(H2O)6]3+ These ions can be present in the solid state e.g. FeSO4.7H2O and Co(NO3)2.6H2O In metal-aqua ions, there are co-ordinate bonds between the metal ions and the water molecules The metal ions are behaving as Lewis acids because they are electron pair acceptors The water molecules are behaving as Lewis bases because they are electron pair donors

2)

Acidity of metal-aqua ions

M2+ solutions are very weakly acidic (pH about 6) due to the following equilibrium: [M(H 2O) 6] 2+ + H 2O [M(H 2O) 5OH] + + H 3O + M3+ solutions are acidic (pH about 3) due to the following equilibrium: [M(H 2O) 6] 3+ + H 2O [M(H 2O) 5OH] 2+ + H 3O + The acidity is caused by an O-H bond breaking in one of the ligands. This is an example of hydrolysis. M3+ solutions are more acidic than M2+ solutions because, in M3+, the metal ion has a greater charge/size ratio which means it has a greater polarising power and more ability to weaken bonds in the water molecules

3)

Reactions with bases a)

NaOH and NH 3(aq) With OH- ions, a precipitation reaction occurs Ammonia solution contains some OH-(aq) produced by the following reaction: NH3(aq) + H2O(l) 4+(aq) + OH-(aq) NH [Cu(H 2O) 6] 2+(aq) + 2OH -(aq) Blue solution [Fe(H 2O) 6] 2+(aq) + 2OH -(aq) Pale green solution [Co(H 2O) 6] 2+(aq) + 2OH -(aq) Pink solution [Fe(H 2O) 6] 3+(aq) + 3OH -(aq) [Cu(H 2O) 4(OH) 2](s) + 2H 2O(l) blue precipitate [Fe(H 2O) 4(OH) 2](s) + 2H 2O(l) green precipitate [Co(H 2O) 4(OH) 2](s) + 2H 2O(l) blue-green precipitate [Fe(H 2O) 3(OH) 3](s) + 3H 2O(l)

Pale violet solution (appears yellow) [Cr(H 2O) 6] 3+(aq) + 3OH -(aq) Red-violet solution [Al(H 2O) 6] 3+(aq) + 3OH -(aq) Colourless solution b) Carbonates

brown precipitate [Cr(H 2O) 3(OH) 3](s) + 3H 2O(l) green precipitate [Al(H 2O) 3(OH) 3](s) + 3H 2O(l) white precipitate

With M2+, the metal carbonate is precipitated e.g. Cu 2+(aq) + CO 32-(aq) Blue solution CuCO 3(s) blue-green precipitate

With the more acidic M3+, carbon dioxide is produced and the metal hydroxide is precipitated e.g.
2[Fe(H 2O) 6] 3+ (aq) + 3CO 32-(aq) 2[Fe(H 2O) 3(OH) 3](s) +3CO 2(g)+ 3H 2O(l)

c)

Amphoteric character Some metal hydroxides, dissolve in both acids and bases. This is called amphoteric character e.g. [Al(H 2O) 3(OH) 3](s) + 3H 3O +(aq) [Al(H 2O) 3(OH) 3](s) + OH -(aq) [Al(H 2O) 6] 3+(aq) + 3H 2O(l) [Al(OH) 4] -(aq) + 3H 2O(l)

[Cr(H 2O) 3(OH) 3](s) + 3H 3O +(aq) [Cr(H 2O) 6] 3+(aq) + 3H 2O(l) [Cr(H 2O) 3(OH) 3](s) + 3OH -(aq) [Cr(OH) 6] 3-(aq) +3H 2O(l)

3)

Ligand substitution reactions

a) With ammonia solution Ammonia and water are similar in size and uncharged. Ligand exchange occurs without change of co-ordination number Firstly, a precipitation reaction occurs (see above). With excess ammonia, the precipitate dissolves. The overall effect is to replace 4 water ligands by ammonias with copper and to replace all 6 water ligands with cobalt [Cu(NH 3) 4(H 2O) 2](aq) + 4H 2O(l) dark blue solution [Co(NH 3) 6] 2+(aq) + 6H 2O(l) straw coloured solution

[Cu(H 2O) 6] 2+(aq) + 4NH 3(aq) Blue solution [Co(H 2O) 6] 2+(aq) + 6NH 3(aq) Pink solution

b)

[Co(NH3)6]2+(aq) is rapidly oxidised by air With concentrated HCl or saturated NaCl(aq)

Chloride is larger than ammonia and water. When Cl- replaces water the coordination number is reduced from 6 to 4 Concentrated HCl and saturated NaCl(aq) are sources of the chloride ligand, Cl[CuCl 4] 2-(aq) + 6H 2O(l) yellow-green solution [CoCl 4] 2-(aq) + 6H 2O(l) blue solution

[Cu(H 2O) 6] 2+(aq) + 4Cl -(aq) Blue solution [Co(H 2O) 6] 2+(aq) + 4Cl -(aq) Pink solution c) Chelate effect

Substitution of a unidentate ligand by a bidentate or multidentate ligand leads to a more stable complex. This is called the chelate effect These reactions have small enthalpy changes because one co-ordinate bond is formed for each co-ordinate bond that is broken. However, the reactions have positive entropy changes because the number of particles increases from left to right [Cu(H 2O) 6] 2+(aq) + EDTA 4-(aq) [CuEDTA] 2-(aq) + 6H 2O(l) 2 particles 7 particles