Redox Processes

Content

• Redox processes: electron transfer and changes in oxidation number (oxidation state)
• Reacting masses and volumes (of solutions and gases)

Learning Outcomes

Candidates should be able to:

• Describe and explain redox processes in terms of electron transfer and/or of changes in oxidation
number (oxidation state)
• Construct redox equations using the relevant half-equations
• Perform calculations, including use of the mole concept, involving volumes and concentrations
of solutions
• Deduce stoichiometric relationships from above calculations

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1. Introduction

Redox reactions or reduction-oxidation reactions are a type of reaction that generally occurs
between a pair of reactants called reducing agents (or reductants) and oxidising agents (or
oxidants).

Oxidizing agents (OA)/ oxidants are the compounds which bring about oxidation.
They themselves will be reduced.

Reducing agents (RA)/ reductants are the compounds which bring about reduction.
They themselves will be oxidised.

The processes of oxidation and reduction happen simultaneously in redox reactions.

Reduction

Oxidising agent + Reducing agent Products

Oxidation

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2. Definitions of Oxidation/Reduction reactions

Definition in terms of: Oxidation Reduction

1. Oxygen gained/lost When a species gains When a species loses
oxygen, it is said to be oxygen, it is said to be
oxidised. reduced.
Example:
Fe2O3 + 3CO → 2 Fe + 3CO2 Carbon in CO is oxidised. Iron in Fe2O3 is reduced.
2. Hydrogen gained/lost When a species loses When a species accepts
hydrogen, it is said to be hydrogen, it is said to be
oxidised. reduced.
Example:
C7H12 + 11 O2 → 7 CO2 + 8 H2O Carbon in heptane is Oxygen is reduced.
oxidised.

3. Electrons gained/lost When a species loses When a species accepts

electrons it undergoes electrons it undergoes
A redox reaction is one in which the
oxidation (LeO). reduction (GeR).
electrons are transferred from one
species to another.
Electrons are being Electrons are being added
removed and appear on the and appear on the LHS of
Example:
RHS of the oxidation half the reduction half equation.
equation.

Reduction half equation:

Oxidation half equation:
Cu2+(aq) + 2e → Cu(s)
Zn(s) → Zn (aq) + 2e
2+

Overall redox equation:

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

➢ An oxidising agent is an electron acceptor and a reducing agent an electron donor.

➢ In a redox reaction, the number of electrons lost = number of electrons gained.
4. Change in oxidation number • the oxidation number • the oxidation number
(ON) of an element is (ON) of an element is
Oxidation number (or oxidation state) increased decreased
indicates the ability of the element in a
species to undergo oxidation.

➢ For ionic compounds, the oxidation number is given a positive or a negative sign to indicate
whether electrons have been added or removed from the atom to achieve the stable set.
➢ For covalent compounds and complex ions, electrons are shared rather than transferred,
oxidation number can be assigned to atoms by giving the more electronegative atom a negative
sign and the less electronegative atom a positive sign.

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2.1 Rules for assigning oxidation numbers

For an atom in a/an… Oxidation Number Examples

element in its free state Always 0 ON of Cl in Cl2 = 0

ON of Fe in Fe = 0

monatomic ion Ion charge ON of Cl in Cl− = -1

ON of Mg in Mg2+ = +2

For compounds and polyatomic ions containing…

Group I metal Always +1 ON of K in K2SO4 = +1

Group II metal Always +2 ON of Ca in CaCO3 = +2

ON of Fe in
Transition metals Roman numeral Iron (III) chloride = +3

ON of Mn in
potassium manganate (VII) = +7

Aluminium Always +3 ON of Al in Al2(SO4)3 = +3

Fluorine Always -1 ON of F in HF = -1
Chlorine, bromine and iodine -1 ON of Br in KBr is -1.
ON of I in HI is -1.
except when combined with a
more electronegative halogen or ON of Cl in ClF3 is +3.
oxygen ON of Cl in ClO2 is +4.

Hydrogen Always +1 ON of H in H2O, HCl, H2SO4 = +1

except in metal hydrides -1 ON of H in NaH, AlH3 = -1

Oxygen Always -2 ON of O in H2O = -2

except in peroxides(-O-O-) -1 ON of O in H2O2 = -1

except in fluorides (fluoride being +2 ON of O in OF2 = +2

more electronegative than
oxygen.)

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 Oxidation Number Examples
The sum of the oxidation
numbers of all atoms in

(i) a neutral compound or Always 0 In H2O, sum of oxidation numbers of H

molecule and O = 2(+1) + (-2) = 0.

(ii) a polyatomic ion is equal to Charge of the ion In MnO4¯, sum of oxidation numbers of
the charge of the ion. Mn and O = (+7) + 4(-2) = -1.

2.2. Oxidation states of Atoms in Covalent Compounds

For a covalently bonded atom, the oxidation number is the charge the atom would possess if the
shared electrons (in the covalent bond) were completely transferred to the more electronegative
atom. This is termed as assigned oxidation state.

Electronegativity is the ability of an atom to attract shared paired of electrons in a covalent bond
(or electron density) towards itself.



H x  Cl :


shared pair of electrons

In a HCl molecule, H and Cl do not have the same attractions for the shared pair of electrons in the
covalent bond. Cl attracts the shared pair of electrons more than H. Cl is therefore more
electronegative than H and has an electronegativity value of 3.0 compared to H having an
electronegativity value of 2.1.

Electronegativity cannot be directly measured and must be calculated from other atomic or molecular
properties. The Pauling scale, on a relative scale running from around 0.7 to 3.98 (hydrogen = 2.20)
is the most common method of comparing relative electronegativities of atoms.

Generally, electronegativity values increase across a Period and decrease down a Group in the
Periodic Table.

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 Increasing Electronegativity

Image source: http://vigorouschemist.hubpages.com/hub/Chemical-Bonding-and-Electronegativity

Examples

Oxidation
Compound/ Ion Structure Remarks
Number of
P atom as an element in its
free state.
P4 P is 0

Cl is more electronegative
H is +1 than H.
HCl
Cl is –1

H is +1
NH3
N is –3

H is +1
CH4
C is –4

When there is a bond between

two same atoms (ie. C-C) in a
molecule, each contributes 0
H is +1 because their
C2H6
C is –3 electronegativities are the
same.

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 H is +1
O is –2
C2H5OH C is –3 and –
1

SO42- ion has a covalent

2- structure.
O O O is -2
SO42-
S S is +6
O O

SO32- has a covalent structure.

2-
O O O is -2
SO32- S S is +4

S4O62- has a covalent

2- structure.
O

O S O
O is -2
S4O62- S
S is +2.5
(tetrathionate ion) S

O S O

2- S2O32- has a covalent

S O structure.
S
S2O32- O is -2
(thiosulfate ion)
O O S is +2

2- S2O82- has a covalent

O
structure.
O S O

S2O82- O
O is -2
(peroxodisulfate
O S is +6
ion)
O S O

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2.3. Using Change in Oxidation Number to Identify Redox Reactions

A redox reaction can be identified when some of the elements undergo a change in oxidation number.

Oxidation occurs when there is an increase in oxidation number of one of the reactant atoms.
Reduction occurs when there is a decrease in oxidation number of one of the reactant atoms.

Example
Cl2 + 2Fe2+ → 2Fe3+ + 2Cl¯

Oxidation number of Cl decreases from 0 in Cl2 to –1 in Cl-. (undergoes reduction)

 Cl2 is the oxidising agent.
Oxidation number of Fe increases from +2 in Fe2+ to +3 in Fe3+. (undergoes oxidation)
 Fe2+ is the reducing agent.
This is a redox reaction.

Example

The reaction between zinc and hydrochloric acid is a redox reaction.

Zn + HCl → ZnCl2 + H2

a) Determine the oxidation numbers of Zn and H in each species

b) Identify which species has been oxidised and reduced and state the oxidising and reducing
agents.

Solution
Zn + HCl → ZnCl2 + H2
Oxidation numbers 0 +1 +2 0

Zinc has been oxidised from Zn to ZnCl2. It is the reducing agent.

Hydrogen chloride has been reduced from HCl to H2. It is the oxidising agent.

Example

For the following reactions,

(i) calculate the oxidation number of the elements in all the reactants and products.
(ii) state with reasons which of the following are redox reactions.

(a) 2 KOH + H2SO4 → K2SO4 + 2 H2O

This is not a redox reaction.
None of the elements showed a change in ON.

(b) Fe3+ + 3OH− → Fe(OH)3

This is not a redox reaction.
None of the elements showed a change in ON.

(c) 3 H2 + N2 → 2 NH3
This is a redox reaction.
The ON of H increased from 0 in H2 to +1 in NH3 and

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 The ON of N decreased from 0 in N2 to -3 in NH3.

(d) 2 CO + O2 → 2 CO2
This is a redox reaction.
The ON of C increased from +2 in CO to +4 in CO2 and
The ON of O decreased from 0 in O2 to -2 in CO2.

(e) Cl2 + 2 OH- → Cl- + ClO- + H2O

This is a redox reaction.
The ON of Cl increased from 0 in Cl2 to +1 in ClO- and
The ON of Cl decreased from 0 in Cl2 to -1 in Cl- .

3. Balancing Redox Equations via the Ionic Half-equations Method

In Acidic Medium In Alkaline and Neutral Mediums

1. Write skeleton ionic half-equations for the 1. Write skeleton ionic half-equations for the
two reactants. two reactants.
2. For each ionic half-equation, balance 2. For each ionic half-equation, balance
number of atoms, other than hydrogen number of atoms, other than hydrogen
and oxygen, if any. and oxygen, if any.
3. (a) Balance oxygen by adding H2O. 3. (a) Balance oxygen by adding H2O.
(b) Balance hydrogen by adding H+. (b) Balance hydrogen by adding H+.
(c) Neutralise all H+ with OH- on both
sides to the equation.
4. Balance the charges for each ionic half- 4. Balance the charges for each ionic half-
equation by adding electrons as equation by adding electrons as
necessary. necessary.
5. Combine the two ionic half-equations after 5. Combine the two ionic half-equations after
equating the electrons. equating the electrons.

Specialist’s Notes

The ionic half equations are essential in later topics such as electrochemistry. Often, candidates
lost marks due to wrong half equations formed in the different conditions such as alkaline and
acidic. Special attention should be paid to this portion as mastery of the skills needed to balance
half equations will serve you well in due course.

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Example

Balance the following redox reactions which occur in acidic medium.

(a) MnO4¯ + Fe2+ → Fe3+ + Mn2+

Solution

[R]: 8H+ + 5e¯ + MnO4¯ → Mn2+ + 4H2O

[O]: Fe2+ → Fe3+ + e¯

Overall: MnO4¯ + 8H+ + 5Fe2+ → Mn2+ + 5Fe3+ + 4H2O

(b) Cr2O72- + SO2 → Cr3+ + SO42-

Solution

[R]: 14H+ + 6e¯ + Cr2O72- → 2Cr3+ + 7H2O

[O]: 2H2O + SO2 → SO42- + 4H+ + 2e¯ (x3)
 6H2O + 3SO2 → 3SO42- + 12H+ + 6e¯

Overall: 2H+ + Cr2O72- + 3SO2 → 2Cr3+ + 3SO42- + H2O

Example

When aqueous KMnO4 is added to a solution of hydrogen peroxide in alkaline medium, a brown
precipitate of MnO2 is formed and O2 gas is evolved. Write a balanced ionic equation for the reaction.

Solution

[R ] : MnO4− + 2H2O + 3e → MnO2 + 4OH− (x2)

 2MnO4− + 4H2O + 6e → 2MnO2 + 8OH−
[O ] : H2O2 + 2OH− → O2 + 2H2O + 2e (x3)
 3H2O2 + 6OH− → 3O2 + 6H2O + 6e

Overall: 2MnO4− + 3H2O2 → 2MnO2 + 2OH− + 2H2O + 3O2

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Example

When aqueous KMnO4 is added to a solution of KBr in alkaline medium, a brown precipitate of MnO 2
is formed and Br- is oxidised to BrO3-. Write a balanced ionic equation for the reaction.

[R]: MnO4¯ + 4H+ + 3e¯ → MnO2 + 2H2O

[O]: Br¯ + 3H2O → BrO3¯ + 6H+ + 6e¯
Overall: 2MnO4¯ + 2H2O + Br¯ → 2MnO2 + H2O + BrO3¯ + 2OH¯
On simplifying: 2MnO4¯ + H2O + Br¯ → 2MnO2 + BrO3¯ + 2OH¯

Disproportionation Reactions

A disproportionation reaction is one where the same substance simultaneously undergoes

oxidation and reduction to give two products.

Disproportionation reactions have some practical significance in everyday life. This a decomposition
reaction of hydrogen peroxide, which produces oxygen and water. Oxygen is present in all parts of
the chemical equation and as a result it is both oxidised and reduced.

2H2O2 (aq) → 2H2O (l) + O2 (g)

In the reactants, the oxidation number of O changes from -1 in H2O2 to -2 in H2O (reduced) and 0 in
O2 (oxidised).

Example

When chlorine gas is bubbled into cold sodium hydroxide solution, it disproportionates into Cl¯ and
ClO¯. Write a balanced equation for this reaction.

Solution

(i) Cl2 + 2e¯ → 2Cl¯

(ii) Cl2 + 2H2O → 2 ClO¯ + 4H+ + 2e¯

Adding 4OH¯ to neutralise the 4H+,
(iii) Cl2 + 2H2O + 4OH¯ → 4H2O + 2ClO¯

(i) + (iii) 2Cl2 + 2H2O + 4OH¯ → 2Cl¯ + 4H2O + 2ClO¯

Simplifying:

Cl2 + 2OH¯ → Cl¯ + H2O + ClO¯

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Example

When chlorine gas is bubbled into hot sodium hydroxide solution, it disproportionates into Cl¯ and
ClO3¯. Write a balanced equation for this reaction.

Solution

(i) Cl2 + 2e¯ → 2Cl¯

(ii) Cl2 + 6H2O → 2ClO3¯ + 12H+ + 10e¯

Adding 12OH¯ to neutralise the 12H+,
(iii) Cl2 + 6H2O + 12OH¯ → 2ClO3¯ + 12H2O + 10e¯

(iv) 5Cl2 + 10e¯ → 10Cl¯ (i) x 5

(iii) + (iv) 6Cl2 + 6H2O + 12OH¯ → 10Cl¯ + 2ClO3¯ + 12H2O

Simplifying:

3Cl2 + 6OH¯ → 5Cl¯ + ClO3¯ + 3H2O

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4. Redox Titrations

There are 2 main types of redox titrations:

(i) Manganate(VII) titration
(ii) Iodine-thiosulfate titration

4.1. Manganate(VII) titration

In acidic medium, KMnO4 is a strong oxidising agent. The ionic half-equation for the reduction of
MnO4¯ ion in acid medium is

MnO4¯ + 8H+ + 5e¯ → Mn2+ + 4H2O

purple (very pale pink)

The manganate(VII) solution is usually added from the burette.

No indicator is required in this titration as KMnO4 is decolorised when it reacts and the end-point is
the very light pink colour when one extra drop of KMnO4 is added to the titrate.

Dilute sulfuric acid is the usual acid used to acidify the solution.
(Nitric acid and hydrochloric acid are not used because nitric acid is an oxidising agent in itself and
hydrochloric acid will be oxidised to Cl2 by manganate.)

KMnO4 can be used to analyse a wide range of reducing agents, e.g.

(i) iron(II) ions

MnO4¯ + 8H+ + 5Fe2+ → Mn2+ + 4H2O + 5Fe3+

*This particular end point is taken to be the first permanent orange colouration due to the
combination of pink manganate(VII) and yellow/brown iron(III).

(ii) ethanedioate ions, C2O42¯ (heat to about 60°C before titrating as the reaction is too slow at
room temperature).

2MnO4¯ + 16H+ + 5C2O42¯ → 2Mn2+ + 8H2O + 10CO2

(iii) hydrogen peroxide

2MnO4¯ + 6H+ + 5H2O2 → 2Mn2+ + 8H2O + 5O2

(iv) nitrite ions, NO2¯ (place the nitrite in the burette and titrate with acidified MnO4¯ in the
conical flask. NO2¯ ions can react with the acidic medium to give NO gas)

2MnO4¯ + 6H+ + 5NO2¯ → 2Mn2+ + 3H2O + 5NO3¯

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Why must manganate titrations be carried out in an acidic medium?

In basic medium, MnO4- is reduced to MnO2 : MnO4- + 2H2O + 3e → MnO2 + 4OH-

The brown MnO2 precipitate interferes with the observation of the end point. Thus it must be
avoided during titrations. This can occur even in neutral solutions or when insufficient acid is
added.

4.2. Iodine-thiosulfate titration

Iodine-Thiosulfate Titration

Sodium thiosulfate, Na2S2O3, is a reducing agent. It is oxidised to the tetrathionate ion, S 4O62-. It
reduces iodine, I2, to iodide, I-.

Equations are as follows:

[O]: 2S2O32- → S4O62- + 2e

[R]: I2 + 2e → 2I-

Overall: 2S2O32- + I2 → S4O62- + 2I-

brown colourless

Colour change at end-point (pale yellow → colourless) is usually not very sharp and starch solution
is used as an indicator for a more distinct colour change (dark blue → colourless).

When starch is used as an indicator, it is not added at the beginning of the titration but half-way
through the titration when the solution is pale yellow. This is because some iodine can be trapped
within the starch molecules if the iodine concentration is high.

Starch is then added and the solution turned dark-blue (due to starch-iodine complex formed) and
the titration can be continued.

End-point occurs when one drop of thiosulfate(VI) decolorises the dark-blue solution.

Specialist’s Notes

This reaction is often used in the topic on kinetics. A clear understanding of this reaction will
definitely help you understand the concepts covered later in that topic. In the chapter of kinetics,
the idea of a homogeneous catalyst will be introduced so that you can understand better how two
negatively charged ions can come together to react with the aid of a homogeneous catalyst.

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Besides iodine itself, Na2S2O3 can be used to analyse a wide range of oxidising agents which can
liberate iodine from KI:

(i) iodate(V) ions

[R] : 2IO3- + 12H+ + 10e → I2 + 6H2O

[O] : 2I- → I2 + 2e

Overall: IO3- + 6H+ + 5I- → 3I2 + 3H2O

(ii) dichromate(VI) ions

+
[R] : Cr2O72- + 14H + 6e → 2Cr3+ + 7H2O
[O] : 2I- → I2 + 2e
Overall: Cr2O72- + 14H+ + 6I- → 2Cr3+ + 7H2O + 3I2

(iii) manganate(VII) ions

[R] : MnO4- + 8H+ + 5e → Mn2+ + 4H2O

[O] : 2I- → I2 + 2e

Overall : MnO4- + 10I- + 16H+ → 2Mn2+ + 5I2 + 8H2O

(iv) copper(II) ions

[R] : 2Cu2+ + 2I- + 2e → Cu2I2

[O] : 2I- → I2 + 2e

Overall: 2Cu2+ + 4I- → Cu2I2 + I2

Example

25.0 cm3 of aqueous potassium iodate(V) reacted with excess acidified potassium iodide solution.
The iodine liberated reacted with 18.00 cm3 of 0.100 mol dm-3 aqueous sodium thiosulfate.

(a) Write the equation between aqueous potassium iodate(V) and acidified potassium iodide.
IO3− + 5I− + 6H+ → 3I2 + 3H2O

(b) Write the equation between the iodine produced and aqueous sodium thiosulfate.

2 S2O32- + I2 → S4O62- + 2 I-

(c) Hence determine how many moles of thiosulfate will be equivalent to 1 mole of aqueous
potassium iodate(V).

From the equations above,

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 1 mol IO3−  3 mol I2 and 1 mol I2  2 mol S2O32-
Hence 1 mol IO3−  6 mol S2O32-

(d) Hence calculate the concentration of the potassium iodate(V) solution.

n(IO3 ) 1
n(S2O3 )2 = 6
[IO3 ] x V(IO3 ) 1
=
[S2O32 ] x V(S2O32 ) 6

[IO3 ] = 0.0120 mol dm-3

5. Solving Problems Involving Redox Reactions

Stoichiometric problems involving redox reactions can be solved using the following steps:

1. Let the unknown oxidation number be x.

2. Write down the necessary redox half equations.
3. Calculate the number of moles of each reactant used.
4. Calculate the number of moles of electrons gained and lost.
5. Find the unknown oxidation number (x) by equating,
number of moles of electrons gained = number of moles of electrons lost

Example 1

A sample of 10 cm3 of 0.10 mol dm-3 iron(II) sulfate is titrated against 0.025 mol dm-3 potassium
manganate(VII) in the presence of an excess of fluoride ions. It is found that 10.0 cm 3 of the
manganate(VII) solution is required to reach the end-point. What is the oxidation number of the
manganese at the end-point?

Solution
Let the oxidation number of the manganese at the end-point be x.

[R]: Mn7+ + 7-x e- → Mnx+ (We simplify the equation by using Mn7+ in place of MnO4-)
[O]: Fe2+ → Fe3+ + e-

n(Mn7+) used = 10.0/1000 x 0.025 = 2.50 x 10-4 mol

n(Fe2+) used = 10.0/1000 x 0.10 = 1.00 x 10-3 mol
n(e-)gained = 2.50 x 10-4 (7-x) mol

n(e-)lost = 1.00 x 10-3 mol

n(e-)gained = n(e-)lost
2.50 x 10-4 (7-x) = 1.00 x 10-3
 x=3

the oxidation number of the manganese at the end-point is +3.

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Example 2

In an experiment, a 0.0100 mol sample of an oxochloride of vanadium, VOClx, required 20.0 cm3 of
0.100 mol dm-3 acidified potassium manganate(VII), KMnO4, for oxidation of the vanadium to its
highest oxidation state of +5.

By calculating the change in oxidation state of the vanadium, deduce the value of x in the formula
VOClx.
Solution

Let unknown oxidation no. of vanadium in VOClx be a.

[R]: MnO4- + 8H+ + 5e- → Mn2+ + 4H2O

[O]: Va+ → V5+ + 5-a e-

n(MnO4-) used = 20.0/1000 x 0.100 = 2.00 x 10-3 mol

n(VOClx) used = 0.0100 mol

n(e-)gained = 5 x 2.00 x 10-3 mol

n(e-)lost = (5 – a) x 0.0100 mol

n(e-)gained = n(e-)lost
5 x 2.00 x 10-3 = (5 – a) x 0.0100
a=4

The oxidation state of V in VOClx is +4.

 +4 + (-2) + x(-1) = 0
x = 2

Specialist’s Notes

Many candidates are often confused with this part of the redox calculations. Always keep in mind
that one substance should be oxidized and the other substance should be reduced. Hence, the
computation of the final oxidation state of the unknown substance should make logical sense.
For example, if the known substance has been oxidised and if your computation shows that the
unknown substance has also been oxidised, it will mean that there must an error in your
computation. Practice will make perfect – do review this part constantly throughout your entire
course of study.

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Summary of Colours of Common Oxidising and Reducing Agents

Oxidising Agents KMnO4 K2Cr2O7

Initial Colour Purple Orange (in acidic medium)
Reduced to Mn2+ (acid medium) Cr3+
or MnO2 (alkali medium)
Final Colour Light pink or black solid Green

Reducing Agents KI Fe2+

Initial Colour Colourless Green
Oxidised to I2 (aq) Fe3+
Final Colour Brown Reddish brown/ yellowish

Specialist’s Notes

You must recognise the colours of the common oxidising and reducing agents. Usually,
decolourisation will be associated with a reduction of the particular oxidising agent. At the same
time, the darkening of colour is commonly linked to an oxidation of the reducing agent. A
common error will be the use of the word “disappearance” instead of decolourisation.
Candidates should be aware that chemistry is not magic at all times.

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