Reactions of Ions in Aqueous Solutions

A LevelAQA

Reactions of Ions in Aqueous Solution

In water, metal ions become hydrated by forming co-ordinate bonds with H2Otext{H}_2text{O} ligands. The metal-aqua ions of aluminium, copper, iron(II) and iron(III) form coloured precipitates when they undergo different reactions. These precipitates are used to identify the metal-aqua ion that is present in a solution.

Metal-Aqua Ions

Metal aqua-ions are complexes that have a central metal ion surrounded by water ligands. They are usually formed by dissolving transition metal salts in an aqueous solution (water). Examples of metal aqua ions include [Cu(H2O)6]2+left[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} and [Al(H2O)6]3+left[text{Al}left(text{H}_2text{O}right)_6right]^{3+}.

[M(H2O)6]2+left[text{M}left(text{H}_2text{O}right)_6right]^{2+} can be formed when M=Fe(II)text{M} = text{Fe(II)} or Cu(II)text{Cu(II)}. [Fe(H2O)6]2+left[text{Fe}left(text{H}_2text{O}right)_6right]^{2+} is green and [Cu(H2O)6]2+left[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} is blue.

[M(H2O)6]3+left[text{M}left(text{H}_2text{O}right)_6right]^{3+} can also be formed when M=Al (III)text{M} = text{Al (III)} or Fe (III)text{Fe (III)}. [Al(H2O)6]3+left[text{Al}left(text{H}_2text{O}right)_6right]^{3+} is colourless and [Fe(H2O)6]3+left[text{Fe}left(text{H}_2text{O}right)_6right]^{3+} is violet.

Acidity
When we talk about the acidity of solutions we usually refer to the transfer of protons, however, it is also possible to describe acidity and basicity in terms of electrons. If a species accepts a lone pair of electrons, it is classed as a Lewis acid. If a species loses a pair of electrons, it can be classified as a Lewis base.

  • Lewis Acid: Electron pair acceptor.
  • Lewis Base: Electron pair donor.

When transition metals form complexes, ligands act as Lewis bases by donating a pair of electrons to the central metal ion while the central metal ion acts as a Lewis acid by accepting the lone pair of electrons.

The acidity of a metal-aqua ion will depend on the charge of the central metal ion. Iron(III) and aluminium form 3+3+ ions which form more acidic solutions than 2+2+ ions formed from iron(II) and copper (II). 3+3+ ions behave as stronger acids because of their higher charge density. Their high charge density means that they have greater polarising power and can therefore more easily release an H+ ions.

A LevelAQA

Reactions with Limited OHtext{OH}^{-} and NH3text{NH}_3

Metal-aqua ions can undergo reaction with limited OHtext{OH}^- and NH3text{NH}_3 to form hydroxide precipitates. In these reactions, OHtext{OH}^- and NH3text{NH}_3 act as Brønsted-Lowry bases by accepting protons from the complex ion.

In limited OHtext{OH}^-, the different metal aqua ions undergo the following reactions. In these reactions, OHtext{OH}^- accepts protons from the H2Otext{H}_2text{O} ligands.

[Fe(H2O)6]2++2OHFe(H2O)4(OH)2+2H2Oleft[text{Fe}left(text{H}_2text{O}right)_6right]^{2+} + 2text{OH}^- rarr text{Fe}left(text{H}_2text{O}right)_4left(text{OH}right)_2 + 2text{H}_2text{O}

[Cu(H2O)6]2++2OHCu(H2O)4(OH)2+2H2Oleft[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} + 2text{OH}^- rarr text{Cu}left(text{H}_2text{O}right)_4left(text{OH}right)_2 + 2text{H}_2text{O}

[Fe(H2O)6]3++3OHFe(H2O)3(OH)3+3H2Oleft[text{Fe}left(text{H}_2text{O}right)_6right]^{3+} + 3text{OH}^- rarr text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3+ 3text{H}_2text{O}

[Al(H2O)6]3++3OHAl(H2O)3(OH)3+3H2Oleft[text{Al}left(text{H}_2text{O}right)_6right]^{3+} + 3text{OH}^- rarr text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3+ 3text{H}_2text{O}

In limited NH3text{NH}_3 the different metal aqua ions undergo very similar reactions to when they react with OHtext{OH}^- ions. However, in limited NH3text{NH}_3, the ammonia ion accepts protons from the H2Otext{H}_2text{O} ligands.

[Fe(H2O)6]2++2NH3Fe(H2O)4(OH)2+2NH4+left[text{Fe}left(text{H}_2text{O}right)_6right]^{2+} + 2text{NH}_3 rarr text{Fe}left(text{H}_2text{O}right)_4left(text{OH}right)_2 + 2text{NH}_4^+

[Cu(H2O)6]2++2NH3Cu(H2O)4(OH)2+2NH4+left[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} + 2text{NH}_3 rarr text{Cu}left(text{H}_2text{O}right)_4left(text{OH}right)_2 + 2text{NH}_4^+

[Fe(H2O)6]3++3NH3Fe(H2O)3(OH)3+3NH4+left[text{Fe}left(text{H}_2text{O}right)_6right]^{3+} + 3text{NH}_3 rarr text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{NH}_4^+

[Al(H2O)6]3++3NH3Al(H2O)3(OH)3+3NH4+left[text{Al}left(text{H}_2text{O}right)_6right]^{3+} + 3text{NH}_3 rarr text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{NH}_4^+

Each metal-aqua forms a different coloured hydroxide precipitate (ppt) when it undergoes these reactions. These colours are used to identify which metal-aqua ion was involved in the reaction.

Fe(H2O)4(OH)2text{Fe}left(text{H}_2text{O}right)_4left(text{OH}right)_2 = Green ppt
Cu(H2O)4(OH)2text{Cu}left(text{H}_2text{O}right)_4left(text{OH}right)_2 = Blue ppt
Fe(H3O)3(OH)2text{Fe}left(text{H}_3text{O}right)_3left(text{OH}right)_2 = Brown ppt
Al(H3O)3(OH)2text{Al}left(text{H}_3text{O}right)_3left(text{OH}right)_2 = White ppt

Metal-Aqua Ion Reaction with Limited OH/NH3text{OH}^{-}/text{NH}_3
[Fe(H2O)]2+left[text{Fe}left(text{H}_2text{O}right)right]^{2+} Fe(H2O)4(OH)2textcolor{#c5e0b4}{text{Fe}left(text{H}_2text{O}right)_4left(text{OH}right)_2}
[Cu(H2O)]2+left[text{Cu}left(text{H}_2text{O}right)right]^{2+} Cu(H2O)4(OH)2textcolor{#0070c0}{text{Cu}left(text{H}_2text{O}right)_4left(text{OH}right)_2}
[Al(H2O)]3+left[text{Al}left(text{H}_2text{O}right)right]^{3+}

Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3

[Fe(H2O)]3+left[text{Fe}left(text{H}_2text{O}right)right]^{3+} Fe(H2O)3(OH)3textcolor{#6b3318}{text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3}
A LevelAQA

Reactions with Excess NH3text{NH}_3 and OHtext{OH}^-

Some metal-aqua ions undergo further reactions when excess NH3text{NH}_3 or OHtext{OH}^- is added to the solution.

Excess OHunderline{text{OH}^-}
In excess sodium hydroxide Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 dissolves and becomes [Al(OH)4]left[text{Al}left(text{OH}right)_4right]^-. In this reaction, the OHtext{OH}^- acts as a Brønsted-Lowry base by accepting the proton from the water ligands. This is shown in the following reaction.

Al(H2O)3(OH)3+OH[Al(OH)4]+3H2Otext{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + text{OH}^- rarr left[text{Al}left(text{OH}right)_4right]^- + 3text{H}_2text{O}

Excess NH3underline{text{NH}_3}
Copper undergoes an incomplete ligand substitution reaction with excess ammonia (NH3)left(text{NH}_3right). There are different theories as to what causes this incomplete ligand substitution to take place but the main thing you need to know is that when this reaction takes place, the precipitate dissolves to form a deep blue solution.

In this reaction, ammonia acts as a Lewis base because it donates its electron pair to the central metal ion. This can be shown through either of the following equations.

Cu(OH)2(H2O)4+4NH3[Cu(NH3)4(H2O)2]2++2H2O+2OHtext{Cu}left(text{OH}right)_2left(text{H}_2text{O}right)_4 + 4text{NH}_3 rarr left[text{Cu}left(text{NH}_3right)_4left(text{H}_2text{O}right)_2right]^{2+} + 2text{H}_2text{O} + 2text{OH}^-
OR
[Cu(H2O)6]2++4NH3[Cu(NH3)4(H2O)2]2++4H2Oleft[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} + 4text{NH}_3 rarr left[text{Cu}left(text{NH}_3right)_4left(text{H}_2text{O}right)_2right]^{2+} + 4text{H}_2text{O}

Amphoteric Salts
Amphoteric salts are salts that can act as both an acid or a base. The aluminium salt, Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3, shows amphoteric character because it reacts and dissolves in both acids and bases.

The reaction that takes place when Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 reacts with excess NaOHtext{NaOH} is an example of how the salt reacts with bases. In acids, Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 undergoes the following reaction:

Al(H2O)3(OH)3+3H+[Al(H2O)6]3+text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{H}^+ rarr left[text{Al}left(text{H}_2text{O}right)_6right]^{3+}

A LevelAQA

Reactions in Carbonate Solutions

In carbonate solutions, metal-aqua ions act as acids. The reaction that a metal-aqua ion will go through will depend upon the charge of the central metal ion. Since metal-aqua with a 2+text{2+} charge are weaker acids than those with a 3+text{3+} charge they undergo a different reaction.

2+text{2+} ions react in a carbonate solution to form insoluble carbonates and water.

[Fe(H2O)6]2++CO32FeCO3+6H2Oleft[text{Fe}left(text{H}_2text{O}right)_6right]^{2+} + text{CO}_3^{2-} rarr text{FeCO}_3 + 6text{H}_2text{O}
FeCO3text{FeCO}_3 will be a green precipitate.

[Cu(H2O)6]2++CO32CuCO3+6H2Oleft[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} + text{CO}_3^{2-} rarr text{CuCO}_3 + 6text{H}_2text{O}
CuCO3text{CuCO}_3 will be a blue/green precipitate.

As 3+3+ metal-aqua ions are stronger acids than 2+2+ ions, they react with carbonates to form water, carbon dioxide and a salt. In this reaction, the production of carbon dioxide gas can lead to bubbles within the solution.

2[Fe(H2O)6]3++3CO32 2Fe(H2O)3(OH)3+3CO2+3H2O2left[text{Fe}left(text{H}_2text{O}right)_6right]^{3+} + 3text{CO}_3^{2-} rarr  2text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{CO}_2 + 3text{H}_2text{O}
Fe(H2O)3(OH)3text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3 forms a brown precipitate.

 

2[Al(H2O)6]3++3CO322Al(H2O)3(OH)3+3CO2+3H2O2left[text{Al}left(text{H}_2text{O}right)_6right]^{3+} + 3text{CO}_3^{2-} rarr 2text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{CO}_2 + 3text{H}_2text{O}
Al(H2O)3(OH)3text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 forms a white precipitate.

A LevelAQA

Reactions of Ions in Aqueous Solutions Example Questions

Question 1: Sodium carbonate solution is added to a solution containing [Al(H2O)6]3+left[text{Al}left(text{H}_2text{O}right)_6right]^{3+} ions.

a.) Write the equation for the reaction that takes place.

b.) State two observations that may be seen when this reaction takes place.

[3 marks]

A Level AQA

a.)

2[Al(H2O)6]3++3CO32−→2Al(H2O)3(OH)3+3CO2+3H2O2left[text{Al}left(text{H}_2text{O}right)_6right]^{3+} + 3text{CO}_3^{2-} rarr 2text{Al}left(text{H}_2text{O}right)_3left(text{OH}right)_3 + 3text{CO}_2 + 3text{H}_2text{O}

b.)White precipitate

Bubbles(/ effervescence/ gas given off)

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Question 2: An aqueous solution reacts with limited NH3text{NH}_3 to form a brown precipitate. Give the formula of the metal-aqua ion involved in this reaction.

[1 mark]

Fe(H2O)3(OH)3text{Fe}left(text{H}_2text{O}right)_3left(text{OH}right)_3

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Question 3: In a reaction, [Cu(H2O)6]2+left[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} reacts with  excess ammonia. In this reaction ammonia acts as a Lewis base rather than a Brønsted-Lowry base. Write an equation for the reaction and state the observation you would make.

A Level AQA

[Cu(H2O)6]2++4NH3→[Cu(NH3)4(H2O)2]2++4H2Oleft[text{Cu}left(text{H}_2text{O}right)_6right]^{2+} + 4text{NH}_3 rarr left[text{Cu}left(text{NH}_3right)_4left(text{H}_2text{O}right)_2right]^{2+} + 4text{H}_2text{O}

The solution would become deep blue.

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Specification Points Covered

AQA A Level –

3.2.6 – Reactions of Ions in Aqueous Solutions