24. Reactions of inorganic compounds in aqueous solutions Flashcards
What is an aqua ion
When a transition metal forms a complex ion with 6 water molecules as ligands
Why is a solution of Fe3+ acidic and Fe2+ not
- Fe3+ ion is smaller and more highly charged than Fe2+
- it is therefore more strongly polarising
- in the [Fe(H2O)6] 3+ (aq) ion the iron strongly attracts electrons from the oxygen atoms
- weakening O-H bonds in the water molecules
- this complex ion will then readily release an H+ ion
- Fe2+ is less polarising so fewer O-H bonds break in solution
What is a hydrolysis reaction
A reaction in which O-H bonds of water are broken and new species are formed
Write an equation for the hydrolysis of [Fe(H2O)6] 3+
[Fe(H2O)6] 3+ (aq) + H2O (l) —-> [Fe(H2O)5(OH)] 2+ (aq) + H3O+ (aq)
The reaction of [Fe(H2O)6] 3+ releasing H+ ions can be described as what reaction
Hydrolysis
Write an equation for the release of H+ ions from [Fe(H2O)6] 3+
[Fe(H2O)6] 3+ (aq)—-> [Fe(H2O)5(OH)] 2+ (aq) + H+ (aq)
In the reaction [Fe(H2O)6] 3+ (aq) + H2O (l) —-> [Fe(H2O)5(OH)] 2+ (aq) + H3O+ (aq) what is the Fe3+ complex acting as
A Bronsted Lowry acid as it is donating a proton (H+) to a water molecule
What are the two examples of [M(H2O)6] 3+
[Fe(H2O)6] 3+
[Al(H2O)6] 3+
What are the two examples of [M(H2O)6] 2+
[Fe(H2O)6] 2+
[Cu(H2O)6] 2+
What happens if you add a base (e.g OH-) to a M2+ or M3+ aqueous complex
It will remove protons from the aqueous complex
What happens if you add a base (e.g OH-) to a M3+ aqueous complex
[M(H2O)6] 3+ (aq) + OH- (aq) —> [M(H2O)5(OH)] 2+ (aq) + H2O (l)
[M(H2O)5(OH)] 2+ (aq) + OH- (aq) —> [M(H2O)4(OH)2] + (aq) + H2O (l)
[M(H2O)4(OH)2] + (aq) + OH- (aq) —-> M(H2O)3(OH)3 (s) + H2O
It becomes a neutral metal (III) hydroxide precipitate
What happens if you add a base (e.g OH-) to a M2+ aqueous complex
[M(H2O)6] 2+ (aq) + OH- (aq) —> [M(H2O)5(OH)] + (aq)
+ H2O (l)
[M(H2O)5(OH)] + (aq) + OH- —> M(H2O)4(OH)2 (s) + H2O (l)
It becomes a neutral metal (II) hydroxide precipitate
What is the precipitate formed when a base (OH-) is added to a M3+ aqueous complex
M(H2O)3(OH)3
What is the precipitate formed when a base (OH-) is added to a M2+ aqueous complex
M(H2O)4(OH)2
Why does iron (III) carbonate not exist but iron (II) carbonate does
- because Fe3+ (aq) is more acidic than Fe2+ (aq)
- carbonate ion is able to remove protons from [Fe(H2O)6] 3+ to form hydrated iron (III) hydroxide
- cannot do this with [Fe(H2O)6] 2+
What is the overall equation for the reaction between iron (III) aqua complex and carbonate ions
2[Fe(H2O)6] 3+ (aq) + 3CO3 2- (aq) —-> 2[Fe(H2O)3(OH)3] (aq) + 3CO2 (g) + 3H2O
What is the overall equation for the reaction between iron (II) aqua complex and carbonate ions
[Fe(H2O)6] 2+ (aq) + CO3 2- (aq) —-> FeCO3 (s) +6H2O
What is the general rule for the formation of carbonates with M2+ and M3+ aqua complexes
In general, carbonates of transition metal ions in oxidation state 2+ exist, whilst those of ions in the +3 state do not
What is the colour of [Fe(H2O)6] 2+
pale green
What is the colour of [Fe(H2O)6] 3+
pale brown
Describe a test to distinguish [Fe(H2O)6] 2+ and [Fe(H2O)6] 3+
- add dilute alkali to both
- the precipitates of both of these complexes are far more distinguishable
- Fe(H2O)3(OH)3 (s) is brown
- Fe(H2O)4(OH)2 is green
What does amphoteric mean
Showing both acidic and basic properties and can react with both acids and bases
What is an example of an amphoteric hydroxide
Aluminium hydroxide
Write an equation for the reaction between HCl and Al(H2O)3(OH)3
Al(H2O)3(OH)3 + 3HCl —> Al(H2O)6 3+ + 3Cl-
Write an equation for the reaction between OH- and Al(H2O)3(OH)3
Al(H2O)3(OH)3 + OH- —-> [Al(H2O)2(OH)4]- + H2O
Name two reasons other ligands would replace water ligands in an aqua ion complex
- the other ligand forms stronger co-ordinate bonds
- the other ligand are present in higher concentration and equilibrium is displaced
List the properties of things that can replace water as a ligand
- water molecules may be replaced by other neutral ligands (e.g ammonia)
- water molecules may be replaced by negatively charged ligands, such as chloride ions
- water molecules may be replaced by bi-or multidentate ligands (chelation)
What happens when a M2+ aqua ion by ammonia
- water molecules are replaced one at a time by ammonia
- [M(H2O)6] 2+ +NH3 —–> [M(NH3)(H2O)5] 2+ + H2O
- [M(NH3)(H2O)5] 2+ + NH3 —-> [M(NH3)2(H2O)4] 2+ H2O
- and so on until
- [M(NH3)6] 2+ is formed
Write the overall equation for the reaction of
[M(H2O)6] 2+ and ammonia
[M(H2O)6] 2+ + 6NH3 [M(NH3)6] 2+ + 6H2O
What is the complication in the reaction between [M(H2O)6] 2+ and ammonia
- ammonia is a base as well a ligand
- so the OH- ions that are in ammonia (aq) might react with the [M(H2O)6] 2+
- a precipitate might form and dissolve
Write the reaction where ammonia reacts as a base with [M(H2O)6] 2+
[M(H2O)6] 2+ (aq) + 2OH- (aq) —> M(H2O)4(OH)2 (s) + 2H2O
M(H2O)4(OH)2 (s) + 6NH3 (aq) —-> [M(NH3)6] 2+ (aq) +4H2O (l) + 2OH- (aq)
Write the equation for the reaction of [Co(H2O)6] 2+ and ammonia (conc.)
[Co(H2O)6] 2+ (aq) + 2NH3 (aq) —> Co(H2O)4(OH)2 + 2NH4+ (aq)
-here ammonia is acted as a base
What is the colour of the precipitate formed when ammonia reacts as a base with [Co(H2O)6] 2+
Blue ppt.
Write an equation if you add more excess ammonia to the products of the reaction between [Co(H2O)6] 2+ and ammonia (conc.)
Co(H2O)4(OH)2 (s) + 6NH3 (aq) —> [Co(NH3)6] 2+ (aq)
4H2O (l) + 2OH- (aq)
Why does ammonia replace water as ligands in Co(H2O)4(OH)2 (s)
- ammonia is a better ligand than water
2. high concentration of ammonia displaces equilibria (displacing both (OH- and H2O))
Describe the observations in the reaction between [Co(H2O)6] 2+ and ammonia
First blue ppt. which then dissolves to form a pale yellow solution.
When aqueous copper ions react with ammonia in aqueous solution ligand replacement is only…
Partial
How many ligands are replace when aqueous copper ions react with ammonia in aqueous solution
4
What is the overall reaction between aqueous copper ions react with ammonia in aqueous solution
[Cu(H2O)6] 2+ + 4NH3 —> [Cu(NH3)4(H2O)2] 2+ + 4H2O
-here ammonia is acting as a base
What is the colour of [Cu(H2O)6] 2+ and [Cu(NH3)4(H2O)2] 2+
[Cu(H2O)6] 2+ is pale blue
[Cu(NH3)4(H2O)2] 2+ is deep blue
What happens in the reaction between ammonia and [Cu(H2O)6] 2+
- ammonia first acts as a base
- the precipitate [Cu(OH)2(H2O)4] (s) is produced
- which is pale blue ppt.
- when more ammonia is added the ppt. dissolves to form [Cu(NH3)4(H2O)2] 2+ (deep blue)
Write the equation for when the ppt. [Cu(OH)2(H2O)4] dissolves in ammonia
[Cu(OH)2(H2O)4] (s) + 4NH3 (aq) [Cu(NH3)4(H2O)2] 2+ (aq) + 2H2O (l) + 2OH- (aq)
What is the shape of [Cu(NH3)4(H2O)2] 2+
- octahedral (as expected for six co-ordinate ion)
- the 4 ammonia molecules exist in square planar
When aqueous copper ions react with concentrated hydrochloric acid there is a change in both…
- charge
- co-ordination number
Write the equation for the reaction between chloride ions and [Cu(H2O)6] 2+
[Cu(H2O)6] 2+ + 4Cl- —> [CuCl4] 2- + 6H2O
What is the colour of [CuCl4] 2-
yellow
Why does [Cu(H2O)6] 2+ have coordination number six and become [CuCl4] 2- with coordination number of only 4
Cl- is larger than H2O so fewer ligands can physically fit around the central copper ion
What is chelation
Formation of complexes with multidentate ligand
What are multidentate ligands
Ligands with more than one lone pair so they can form more than one co-ordinate bond
Give 3 examples of multidentate ligands
- ethylene diamine
- benzene- 1,2-diol
- EDTA 4-
Why are complexes usually more stable with multidentate ligands than monodentate ligands
There is a positive entropy change of the reaction
What can ethylene diamine be represented as
en
Write the equation for the reaction between en and [Cu(H2O)6] 2+
[Cu(H2O)6] 2+ (aq) + 3en —> [Cu(en)3] 2+ (aq) + 6H2O
4 entities to 7 meaning big increase in entropy
Write the equation for the reaction between en and [Cu(H2O)6] 2+ (aq) and EDTA 4-
[Cu(H2O)6] 2+ (aq) + EDTA 4- (aq) —-> [CuEDTA] 2- (aq) + 6H2O
Reaction between OH- and [Fe(H2O)6] 2+ (aq)
- green ppt.
- [Fe(H2O)4(OH)2]
Reaction between OH- and [Cu(H2O)6] 2+ (aq)
- pale blue ppt.
- [Cu(H2O)4(OH)2]
Reaction between NH3 and [Fe(H2O)6] 2+ (aq)
- green ppt.
- [Fe(H2O)4(OH)2]
Reaction between little NH3 and [Cu(H2O)6] 2+ (aq)
- pale blue ppt.
- [Cu(H2O)4(OH)2]
Reaction between excess NH3 and [Cu(H2O)6] 2+ (aq)
- deep blue solution
- [Cu(NH3)4(H2O)2] 2+
Reaction between CO3 2- and [Fe(H2O)6] 2+ (aq)
- green ppt.
- FeCO3
Reaction between CO3 2- and [Cu(H2O)6] 2+ (aq)
- green/blue ppt.
- CuCO3
Reaction between OH- and [Fe(H2O)6] 3+ (aq)
- brown ppt.
- [Fe(H2O)3(OH)3]
Reaction between little OH- and [Al(H2O)6] 3+ (aq)
- white ppt.
- [Al(H2O)3(OH)3]
Reaction between excess OH- and [Al(H2O)6] 3+ (aq)
- colourless
- [Al(OH)4-]
Reaction between NH3 and [Fe(H2O)6] 3+ (aq)
- brown ppt.
- [Fe(H2O)3(OH)3]
Reaction between NH3 and [Al(H2O)6] 3+ (aq)
- white ppt.
- [Al(H2O)3(OH)3]
Reaction between CO3 2- and [Fe(H2O)6] 3+ (aq)
- brown ppt.
- [Fe(H2O)3(OH)3]
- and CO2 bubbles
Reaction between CO3 2- and [Al(H2O)6] 3+ (aq)
- white ppt.
- [Al(H2O)3(OH)3]
- and bubbles of CO2