REDOX REACTIONS

Specification Points Covered

5.2.3 Redox and Electrode Potentials
(b) Construction of redox equations using half-equations and oxidation numbers
(c) Interpretation and prediction of reactions involving electron transfer

Constructing Full Equations

A redox reaction can be constructed from two half-equations; one representing an
oxidation process, and the other a reduction process.

Constructing a Full Equation from Half-Equations

Mg  Mg2+ + 2e–
Cu2++ 2e–  Cu

1. Balance the electrons

Make the number of electrons in each half-equation equal — multiply each half-
equation so that the number of electrons is the same in both half-equations:
Mg  Mg2+ + 2e–
Cu2++ 2e–  Cu

2. Combine the equations

Combine the left-hand sides and right-hand sides of each half-equation:

Mg + Cu2++ 2e–  Mg2+ + 2e– + Cu

3. Cancel the electrons

The electrons are balanced as the same number of electrons is found on both sides.
Therefore, the electrons can just cancel out:
Mg + Cu2+  Mg2+ + Cu

4. Check the charge balance and stoichiometry

Confirm that the charge is conserved and that the equation is correctly balanced.

snaprevise.co.uk 1
 Worked Example: Redox Equations
Construct a redox equation from the following half-equations:
MnO4– + 8H+ + 5e–  Mn2+ + 4H2O
Fe2+  Fe3+ + e–

Solution
1. Make the number of electrons in each half-equation equal:
The half-equation involving Mn has 5 electrons, whereas the half-equation
involving Fe has only 1 electron

Therefore, to make the number of electrons in each half-equation equal, multiply

the half-equation involving Fe by 5 to give 5 electrons — the same number of
electrons as in the half-equation involving Mn
5Fe2+  5Fe3+ + 5e-

2. Combine the equations:

MnO4– + 8H+ + 5e– + 5Fe2+  5Fe3+ + 5e– + Mn2+ + 4H2O

3. Cancel the electrons:

MnO4– + 8H+ + 5Fe2+  5Fe3+ + Mn2+ + 4H2O

4. Check the charge balance and stoichiometry:

(–1) + 8(+1) + 5(+2) = +17 = 5(+3) + (+2)

Using Oxidation Numbers

There are some rules that determine what the oxidation state a species will adopt in
a reaction. This was covered in more detail in the ‘Oxidation Numbers’ section.

Rules for Assigning Oxidation Numbers:

• An element in its standard state has an oxidation number of zero
• Metals tend to be oxidised
• Non-metals tend to be reduced
• Hydrogen usually has an oxidation number of 1
• Oxygen usually has an oxidation number of –2

Exceptions to these rules include hydrogen in metal hydrides (oxidation number of –1)
and oxygen in peroxides (oxidation number of –1).

These rules can be used to construct a full balanced redox equation.

snaprevise.co.uk 2
Worked Example: Constructing Redox Equations
Construct a redox equation for the reaction between iron(II) and acidified
manganate(VII) ions to form Mn2+ and Fe3+ ions.

Solution
1. Write down what we know from the question:
Fe2+ + H+ + MnO4–  Mn2+ + Fe3+
The H+ ions are present due to the mixture being acidified.

2. Consider the species being reduced:

MnO4–  Mn2+
We know from the question that the Mn in MnO4– has an oxidation number of +7:
Mn7+  Mn2+
These two oxidation states of Mn have a charge difference of five. This means that
five electrons need to be added to the more positive side in order to balance out
the charges.

3. Add in the electrons:

Fe2+ + H+ + MnO4– + 5e–  Mn2+ + Fe3+

4. If needed, form water to balance the oxygen and hydrogen:

Fe2+ + 8H+ + MnO4– + 5e–  Mn2+ + Fe3+ + 4H2O
4 oxygens
The number of H+ ions has been increased to eight, as adding the water molecules to
balance the oxygens introduced eight hydrogen atoms.

5. Consider the species being oxidised:

Fe2+  Fe3+ + e–
An electron needs to be added to the more positive side to balance the charge.
As there are five electrons in the reduction equation, there also needs to be five
electrons in the oxidation equation for the electrons to balance and cancel.
5Fe2+  5Fe3+ + 5e–

6. Combine the equations:

MnO4– + 8H+ + 5e– + 5Fe2+  5Fe3+ + 5e– + Mn2+ + 4H2O

7. Cancel the electrons:

MnO4– + 8H+ + 5Fe2+  5Fe3+ + Mn2+ + 4H2O

8. Check the charge balance and stoichiometry:

(–1) + 8(+1) + 5(+2) = +17 = 5(+3) + (+2)

snaprevise.co.uk 3
Specification Points Covered
5.2.3 Redox and Redox Potentials: Redox Titrations
(d) The techniques and procedures used when carrying out redox titrations including those involving Fe2+/MnO4–
and I2/S2O32– (see also 2.1.5 e–f)
(e) Structured and non–structured titration calculations, based on experimental results of redox titrations involving:
(i) Fe2+/MnO4– and I2/S2O32–
(ii) Non–familiar redox systems
○○ Non–structured titration calculations could be examined in the context of both acid–base and redox
titrations (see also 2.1.4 d–e)

Titrations
Redox titrations can show how much oxidising agent is needed to react exactly with
a  reducing agent. Redox titrations are similar to acid–base titrations but also have
some fundamentaldifferences.

• If we know the volume in the conical flask, the

reaction equation, and the concentration of the
substance in the burette, we can calculate the
concentration of the substance in the conical flask
• Transition metals have variable oxidation states,
so they are often present in either the oxidising or
reducing agent
• Their colour changes also make them easy to use in
titrations as it is normally easy to see the endpoint

Manganate (VII) Ions as an Oxidising Agent

Manganate(VII) ions are readily reduced to Mn2+ ions under acidic conditions. The MnO4–
ions are a different colour to the Mn2+ ions (MnO4– ions are purple, Mn2+ are colourless).
The other chemical used in this titration must be a reducing agent.

Half–Equations for Iron(II) and Manganate(VII) Titration

Oxidation: Fe2+ → Fe3+ + e–
Reduction: 8H+ + MnO4– + 5e–→ Mn2+ + 4H2O
Overall: 8H+ + MnO4– + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+

snaprevise.co.uk 4
 Worked Example: Calculations with Redox Titrations
21.60 cm3 of 0.015 mol dm–3 KMnO4 is added to 30.00 cm3of a solution containing
an unknown amount of iron(II) ions, and at this point, the solution changes from
colourless to purple.
What was the concentration of iron (II) in the solution before the titration?

Solution
1. Find the number of moles of MnO4– that reacted:
Ensure that you convert volume from cm3 to dm3

2. Use the reaction equation to find the number of moles of Fe2+ present:
For every one mole of manganate that is used up, five moles of iron(II) are used up.
Therefore, we multiply the number of moles we have just calculated by five:

3. Find the concentration of the solution:

Iodine–Thiosulphate Titrations
In iodine–thiosulphate titrations, iodine is usually reduced to form iodide ions whilst
the thiosulphate ions are oxidised. Iodine is often combined with starch, which makes
it dark blue.

Oxidation: 2S2O32– (aq) → S4O62– (aq) + 2e–

Reduction: I2 (aq) + 2e– → 2I– (aq)
Overall: 2S2O32– (aq) + I2 (aq) → S4O62– (aq) + 2I– (aq)

Starch is used in this reaction to highlight the end point. When all the iodine is used up,
the starch returns to its normal pale straw yellow colour.

This titration is often used to work out the concentration of an oxidising agent. This is
possible because the oxidising agent can oxidise the excess I– ions.

This allows us to calculate the amount of I2 present.

snaprevise.co.uk 5
Worked Example: Iodine Thiosulphate Titrations
A sample of aqueous bromine solution is mixed with an equal volume of excess
potassium iodide and starch. The bromine acts as an oxidising agent.
14.50 cm3 of 0.20 mol dm–3 Na2S2O3 is then added to 15 cm3 of the new solution
and at this point, the solution changes colour from inky blue to pale straw yellow.
Calculate the concentration of bromine molecules after the potassium iodide was
added.

Solution
1. Write the half equations for the reaction:
Br2 (aq) + 2e– → 2Br– (aq)
2I– (aq) → I2 (aq) + 2e–

2. Construct the full reaction equation:

Br2 (aq) + 2I– (aq) → 2Br– (aq) + I2 (aq)

3. Find the number of moles of S2O32– that reacted in the titration:

4. Use the titration equation to calculate the number of moles of I2 present:

2S2O32– (aq) + I2 (aq) → S4O62– (aq) + 2I– (aq)
Ratio is 2:1

5. Use the reaction equation for the oxidising agent and iodide ions to find the
number of moles of the oxidising agent needed to form the iodide ions:
Br2 (aq) + 2I– (aq) → 2Br– (aq) + I2 (aq)
Ratio is 1:1

6. Calculate the concentration of the oxidising agent:

EXAM TIP
Remember OILRIG when you are writing redox equations.
The first step for completing any redox titration question is to figure out the
reaction equation. You can do this by figuring out the half equations, then
combining them.

snaprevise.co.uk 6
Unfamiliar Titrations
It is important to be able to apply the general method of redox titration calculations to
unfamiliar situations. Below is a standard example, and the same method can be used
in almost every titration question.

Chromate ions, (Cr2O72–) will also oxidise Fe2+. This titration can also be used to find the
concentration of iron (II).

Half–Equations for Iron(II) and Dichromate(VI) Titration

• Oxidation: Fe2+ → Fe3+ + e–
• Reduction: Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7H2O
• Overall: 14H+ + Cr2O72– + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+

There is not a clear colour change at this end point, so an indicator is used.

Worked Example: Calculations with Redox Titrations

In the presence of an oxidising agent, hydrogen peroxide undergoes the following
reaction:
H2O2 (aq) → 2H+ (aq) + O2 (g) + 2e–

20 cm3 of a solution containing hydrogen peroxide is titrated with potassium

permanganate, and it is found that 18.62 cm3 of 0.015 mol dm–3 potassium
permanganate solution was required for complete oxidation of the hydrogen peroxide.
Calculate the concentration of the hydrogen peroxide solution.

Solution
1. Write the half equations for the reaction:
Reduction: 8H+ + MnO4– + 5e–→ Mn2+ + 4H2O
Oxidation: H2O2 → 2H+ + O2 + 2e–

2. Write the full equation for the reaction and cancel the excess H+ to balance:
6H+ + 2MnO4– + 5H2O2 → 2Mn2+ + 8H2O + 5O2

3. Find the number of moles of MnO4– that reacted in the titration:

4. Use the titration equation to calculate the number of moles H2O2 present:
Ratio is 2:5

5. Work out the concentration:

snaprevise.co.uk 7
Redox Titrations in Alkaline Solution
To convert an equation for the reaction in acidic conditions to one in alkaline conditions,
OH– ions are added to both sides of the equation.

Worked Example: Alkaline Redox Equations

Below is the redox equation for the reaction of iron(II) with permanganate ions in
acidic conditions.
Use this equation to work out the redox equation when the reaction occurs under
alkaline conditions:
8H+ + MnO4– + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+

Solution
1. The hydrogen ions on the left–hand side of the equation need to be neutralised:
To do this, eight OH– ions are added to both sides of the equation:

8OH– + 8H+ + MnO4– + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+ + 8OH–

2. Now, the hydrogen ions and hydroxide ions can be combined to form water
molecules:
8H2O + MnO4– + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+ + 8OH–

3. Now there is an excess of hydroxide ions, no H+ ions and the reaction is in alkaline
conditions. All that is left to do is to cancel the excess water molecules. This can be
done because there are water molecules on both sides of the equation:
4H2O + MnO4– + 5Fe2+ → Mn2+ + 5Fe3+ + 8OH–

snaprevise.co.uk 8