Redox Reactions and Reactivity of Halogens Revision notes | A-Level Chemistry OCR

Redox Reactions and Reactivity of Halogens

This lesson covers:

How halogens gain electrons to become ions
Trends in reactivity down the group
Displacement reactions between halogens and halide ions
Identification of halogens based on colour changes in displacement reactions

Halogens form 1- ions by gaining electrons

Halogens react by gaining an electron to form negative ions with a 1- charge (known as halide ions). For example:

X + e⁻ ➔ X⁻

Where X represents a halogen atom.

This electron gain results in the halogen being reduced, as its oxidation number decreases from 0 to -1.

As the halogen gains an electron, it causes another substance to be oxidised - so halogens act as oxidising agents

Reactivity decreases down group 7

The reactivity of the halogens decreases going down the group because:

Atomic radius increases down the group as more electron shells are added.
The increasing size leads to the outer electrons being farther from the positive nucleus.
The outer electrons also experience more shielding from inner electron shells.
The electrostatic attraction between the outer electrons and nucleus gets progressively weaker.
The increase in atomic radius and shielding outweigh the increase in nuclear charge so it becomes harder for larger halogens to attract the electron needed to form a negative ion.

Halogens displace less reactive halide ions

The relative reactivity of the halogens can be seen in displacement reactions.

If an aqueous halogen solution is added to a solution containing halide ions, a more reactive halogen will displace a less reactive halide from the solution.

The displacing halogen is reduced as it gains an electron to form the halide ion
The displaced halide is oxidised as it loses an electron to form the halogen molecule

The rule is: a halogen will displace any halide ion below it in group 7.

Here is a summary table including the ionic equations for the displacement reactions:

Halogen	Displaces	Ionic equation(s)
Chlorine (Cl $_{2}$ )	Bromide (Br $^{-}$ ) and Iodide (I $^{-}$ )	Cl $_{2 (a q)}$ {2(aq)} + 2Br $^{-}$ $_{(a q)}$ {(aq)} ➔ 2Cl $^{-}$ $_{(a q)}$ + Br $_{2 (a q)}$ / Cl $_{2 (a q)}$ {2(aq)} + 2I $^{-}$ $_{(a q)}$ ➔ 2Cl $^{-}$ $_{(a q)}$ {(aq)} + I $_{2 (a q)}$
Bromine (Br $_{2}$ )	Iodide (I $^{-}$ )	Br $_{2 (a q)}$ {2(aq)} + 2I $^{-}$ $_{(a q)}$ ➔ 2Br $^{-}$ $_{(a q)}$ {(aq)} + I $_{2 (a q)}$
Iodine (I $_{2}$ )	None	No reaction

This table shows that reactivity decreases down group 7 because:

Chlorine can oxidise both bromide and iodide, showing it is the most reactive.
Bromine can oxidise iodide but not the more reactive chloride, so bromine has medium reactivity.
Iodine cannot oxidise either chloride or bromide, so it is the least reactive.

Colour changes in halogen displacement reactions

When a more reactive halogen displaces a less reactive halide ion in solution, visible colour changes occur that allow the halogen product to be identified.

Colour changes in aqueous solution

When halogens displace less reactive halide ions in aqueous solution, visible colour changes occur if a reaction takes place:

If bromide (Br^-) is displaced, forming bromine (Br₂), the aqueous solution turns yellow
If iodide (I^-) is displaced, forming iodine (I₂), the aqueous solution turns orange/brown
If no reaction occurs, the aqueous solution remains colourless

These colour changes allow the halogen present to be identified.

	Potassium chloride (KCl)	Potassium bromide (KBr)	Potassium iodide (KI)
Chlorine (Cl $_{2}$ )	N/A	Yellow (Br $_{2}$ )	Orange/brown (I $_{2}$ )
Bromine (Br $_{2}$ )	No colour change (no reaction)	N/A	Orange/brown (I $_{2}$ )
Iodine (I $_{2}$ )	No colour change (no reaction)	No colour change (no reaction)	N/A

Colour changes in organic solution

The halogen products can be more clearly visualized by using an organic solvent like cyclohexane. After the reaction, shaking the aqueous layer with hexane will result in the halogen dissolving in the organic layer. This separates out on top of the aqueous solution:

If bromide (Br^-) is displaced, forming bromine (Br₂), the organic layer turns orange
If iodide (I^-) is displaced, forming iodine (I₂), the organic layer turns purple
If no reaction occurs, the organic solution remains colourless

	Potassium chloride (KCl)	Potassium bromide (KBr)	Potassium iodide (KI)
Chlorine (Cl $_{2}$ )	N/A	Orange (Br $_{2}$ )	Purple (I $_{2}$ )
Bromine (Br $_{2}$ )	No colour change (no reaction)	N/A	Purple (I $_{2}$ )
Iodine (I $_{2}$ )	No colour change (no reaction)	No colour change (no reaction)	N/A

So the halogen products can be clearly identified based on the colour changes in both aqueous and organic layers after the displacement reactions.