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H2 Chemistry Notes

H2 Chemistry (9729)
Lecture Notes 2
Redox Reactions
Assessment Objectives:
Candidates should be able to:
(a) describe and explain redox processes in terms of electron transfer and/or of changes in oxidation
number (oxidation state)
(b) interpret redox reactions in terms of changes in oxidation state of the species involved
(c) predict oxidation number in a species based on experimental data
(d) construct and balance redox equations using the relevant half-equations
(e) describe and explain the use of Fe3+/Fe2+, MnO4–/Mn2+ and Cr2O72–/Cr3+ as examples of redox
systems
(f) perform calculations involving redox reactions

Content
 Introduction
 Oxidation Number (O.N.) / Oxidation State
 Redox Reactions
 Redox Titrations
Recommended Materials:
1) Cambridge International AS and A Level Chemistry by Peter Cann and Peter Hughes, published by
Hodder Education
2) A-Level Chemistry (4th Edition) by E N Ramsden, published by Oxford University Press
3) Advanced Study Guide Chemistry by C S Toh, published by Step-by-Step International Pte. Ltd.

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1. Introduction
1.1 Definitions of Reduction / Oxidation

- The term “redox” is used as an abbreviation for the processes of reduction and oxidation which
occur simultaneously. A redox reaction is an oxidation-reduction reaction.
- There are different ways to define oxidation and reduction.

a. Loss/gain of Oxygen - Oxidation is gain of oxygen.

- Reduction is loss of oxygen.
- E.g.
reduction

Fe2O3 + 3CO 2Fe + 3CO2

oxidation
b. Loss/gain of Hydrogen - Oxidation is loss of hydrogen.
- Reduction is gain of hydrogen.

oxidation
- E.g. CH3CH2OH CH3CHO

CH3CHO reduction CH3CH2OH

c. Loss/gain of electrons - Oxidation is loss of electrons.
- Reduction is gain of electrons
- E.g.
Oxidation: Zn (s) → Zn2+ (aq) + 2e
Reduction: Cu2+ (aq) + 2e → Cu (s)
Overall: Zn (s) + Cu2+ (aq) → Zn2+ (aq) + Cu (s)

d. Increase/decrease in oxidation - Oxidation is increase in oxidation number.

number (oxidation state) - Reduction is decrease in oxidation number.
-2
Reduction
E.g. 2Mg(s) + O2(g) 2Mg2+O2(s)

Oxidation

Tips to remember:

OIL RIG - Oxidation Is Loss (of electrons), Reduction Is Gain (of Electrons)

LEO GER – Loss of Electron (Oxidation), Gain of Electron (Reduction)

- Oxidising agent/ oxidant is one which causes the oxidation of others while itself is reduced.

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- Reducing agent/ reductant is one which causes the reduction of others while itself is oxidised.
RED – Reducing agent (Electron Donor)

Summary:

Oxidation is defined as Reduction is defined as

1. gain of oxygen 1. loss of oxygen
2. loss of hydrogen 2. gain of hydrogen
3. loss of electrons 3. gain of electrons
4. increase in oxidation state 4. decrease in oxidation state

2. OXIDATION NUMBER (O.N) / OXIDATION STATE

- An oxidation number is a number which is assigned to an element in a substance to show its
state of oxidation.
- In assigning oxidation numbers to atoms in a compound, it is assumed that all compounds
are ionic and the oxidation number is the charge of the atom.
- It is generally equal to the number of electrons lost (positive oxidation number) or gained
(negative oxidation number) or shared by their atoms during bond formation.
- When electrons are shared, the more electronegative atom should be assigned the
negative oxidation number while the less electronegative atom should be assigned the positive
oxidation number.
- An atom is oxidized if its oxidation number increases. An atom is reduced if its oxidation
number decreases.
- When two identical atoms are bonded to each other, we do not consider the shared
electrons.
- Oxidation number can be zero, positive, negative, a whole number or a fraction.
- REMEMBER: Oxidation state should have a sign (+ or -) if it is not 0.

2.1 Rules for Assigning Oxidation Number

1. The oxidation number of an atom in the elemental state = 0

E.g: Ca, I2, S8¸ P4 have oxidation number of 0

2. The oxidation number of monoatomic ion is simply the charge on the ion.

Ions Oxidation number

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Cl- -1
Mg2+ +2
Fe3+ +3

3. Some elements almost always have the same O.N. in all their compounds. They are used as
reference points in assigning O.N. to other elements.

Element Common oxidation number Exception

Hydrogen +1 -1 in metal hydrides, such as NaH, MgH2
Group I +1 -
Group II +2 -
Fluorine -1 -
Oxygen -2 -1 in peroxides, such as H2O2, BaO2 (barium peroxide)
*Peroxide ion is O22-
- ½ in KO2 (potassium superoxide*)
*Superoxide ion is O2-
+2 in OF2
(since F is more electronegative than O)
Chlorine -1 Except when forming compounds with more electronegative
atom
E.g. O.S. for Cl in ClO2 = +4
O.S. for Cl in ClF = +1
- The electronegativity of an atom is the ability of
the atom in a molecule to attract shared electrons in a
bond.
- Electronegativity generally increases across a
period and decreases down a group.
- E.g. Electronegativity decreases in the order:
F > O > Cl > N > C > H
- Electronegativity values can be found at:
http://www.rsc.org/periodic-table/trends
Aluminium +3 -

4. The sum of the oxidation number of all the atoms or ions in a neutral compound = 0.

Compound O.N.
KCl +1+ (-1) = 0
CaBr2 +2 + 2(-1) = 0
Al2O3 2(+3) + 3(-2) = 0
HI +1 + (-1) = 0
H2S 2(+1) + (-2) = 0
Note: Consider covalent compounds to be wholly ionic.

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5. The sum of the oxidation number of all the atoms in a polyatomic ion = charge on the ion.

Example:

SO42- : The sum of the oxidation numbers (O.N of S = +6, O.N. of O = -2)

= +6 + 4(-2) = - 2

= charge on the ion

CrCl63- : The sum of the oxidation numbers (O.N of Cr = +3, O.N. of Cl = -1)

= +3 +6(-1) = -3

= charge on the ion

Note:

- In assigning O.N., the more electronegative atom should be assigned the negative sign.
- In the Periodic Table, electronegativity increases across the period and decreases down the group.
- The most electronegative atom is F, followed by O then N. (Refer to Atomic Structure)
- Oxidation number of Mg in Mg2+ = +2 (the “+” sign precedes the number “2”)
Charge on Mg2+ ion = 2+ (the “+” sign is written after the number “2”)
Exercise 1:

(a) Assign oxidation numbers to all atoms in the following ions/compounds:

TlCl3 Tl:+3 Cl: -1 SO32- S: +4 O: -2

MnO4- Mn: +7 O: -2 AlH3 Al: +3 H: -1

MnO2 Mn: +4 O: -2 ClO3- Cl: +5 O: -2

H2O2 H: +1 O: -1 NH4+ N: -3 H: +1

(b) What is the oxidation number of the underlined element?

(i) Cr(CN)63- : +3 (ii) Fe(OH)2 : +2
2+
(iii) [Cu(NH3)4] : +2 (iv) Cr2O72- : +6

2.2 Predicting Oxidation Number in a Species Based on Experimental Data

Example 1: 1 mole of ClO4- oxidises 8 moles of Ti3+ to Ti4+. What is the final oxidation state of Cl in the
product? (Given: Ti3+ → Ti4+ + e)

Solution: 1 mole of Ti3+ loses 1 mole of electron when oxidised to Ti4+

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8 moles of Ti3+ lose 8 moles of electrons when oxidised to Ti4+

8 moles of electrons must be gained by 1 mole of ClO4-

Since O.S. of Cl in ClO4- is +7,

After gaining electrons, new O.S. of Cl = +7 - 8 = -1

Example 2: 1 mole of S2O32- ion reduces 4 moles of Cl2 molecules. What is the sulfur containing product
of this reaction?

A S B SO2 C SO42- D S4O62-

Solution: Cl2 + 2e → 2Cl-

4 moles of Cl2 gain 8 moles of electrons when reduced to Cl-

8 moles of electrons must be lost by 1 mole of S2O32-

Since 1 mole of S2O32- contains 2 moles of S atoms,

1 mole of S loses 4 moles of electrons

Since O.S. of S in S2O32- is +2,

After losing electrons, new O.S. of S = +2 + 4 = +6

Example 3: In an experiment, 25.0 cm3 of 0.15 mol dm-3 solution of metallic salt reduces exactly 23.40
cm3 of 0.4 mol dm-3 solution of bromine. If the original oxidation number of the metal in the
salt was +1, what would be the new oxidation number of the metal?

Solution: No of moles of metallic salt = 25/1000 x 0.15 = 3.75 x 10-3 mol

No of moles of Br2 = 23.40/1000 x 0.4 = 9.36 x 10-3 mol

Mole ratio of Br2: metallic salt = 5 : 2

Br2 + 2e → 2Br-

5 moles of Br2 gain 10 moles of electrons when reduced.

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2 moles of metallic salt lose 10 moles of electrons when oxidised.

1 mole of metallic salt loses 5 moles of electrons when oxidised.

Since O.S. of metal in metallic salt is +1,

after losing electrons, new O.S. of metal = +1 + 5 = +6

3. REDOX REACTIONS
 Reactions involving oxidation always occur simultaneously with reduction and these
reactions are termed REDOX reactions.
 There is no net change in the number of electrons in a redox reaction, i.e. electrons lost by
the oxidised species must be taken in by the reduced species.

3.1 Types of Redox Reactions

- In general, to decide whether a reaction is a redox reaction, assign oxidation numbers to the
atoms in the reactants and products, and check for any changes in oxidation numbers.
- Note: In a redox reaction, total increase in oxidation number = total decrease in oxidation number

1. Reaction of a metal with an acid

E.g: 2HCl(aq) + Mg(s) → MgCl2(aq) + H2(g)

2. Reaction of a metal with a non-metal

E.g: 2Fe(s) + 3Cl2(g) → 2FeCl3(s)

3. Reaction of a metal with water

E.g: Ca(s) + 2H2O(l) → Ca(OH)2(aq) + H2(g)

4. Reactions at the electrodes during electrolysis

E.g: Electrolysis of liquid lead(II) bromide:

Cathode (-): Pb2+(l) + 2e → Pb(s) ; Anode (+): 2Br-(l) → Br2(l) + 2e

5. Displacement reactions

E.g: Cl2(aq) + 2Br-(aq) → Br2(aq) + 2Cl- (aq)

6. Disproportionation reactions

A redox reaction is a reaction in which the same element is simultaneously reduced and oxidised.

E.g: 2Cu+(aq) → Cu2+(aq) + Cu(s)

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3NaClO(aq) → 2NaCl(aq) + NaClO3(aq)

Examples of Non-Redox Reactions

1. Precipitation reactions:
Ag+(aq) + Cl-(aq) → AgCl(s)
2. Neutralisation reactions:
H+(aq) + OH-(aq) → H2O(l)
3. Complex formations:
Cu2+(aq) + 4Cl-(aq) → [CuCl4]2-(aq)
4. Condensation:
2CrO42-(aq) + 2H+(aq) → Cr2O72-(aq) + H2O(l)

Exercise 2:
Which of the following are redox equations? Identify the oxidising and reducing agents and write down
the change in oxidation number where applicable.
(a) 2Na(s) + 2HCl(aq) → 2NaCl(aq) + H2(g)
Oxidation Reduction
Na: 0 H in HCl: +1
Na in NaCl: +1 H in H2: 0
Reducing agent: Na Oxidising agent: HCl

(b) NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

Not a redox equation

(c) 2H2O2(aq) → 2H2O(l) + O2(g)

Oxidation Reduction
O in H2O2: -1 O in H2O2: -1
O in O2: 0 O in H2O: -2
Reducing agent: H2O2 Oxidising agent: H2O2

Which of the above equations is an example of disproportionation reaction?

Part (c). H2O2 is both reduced to water and oxidised to oxygen.

3.2 Balancing Redox Equations

All balanced equations must satisfy two criteria:

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1) There must be mass balance, i.e., the same number of atoms of each kind must be shown as
reactants and products.

2) There must be charge balance. The sum of actual charges on the left and right sides of the
equation must be equal.

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3.2.1 The Half Equation Method

1. In aqueous / acidic solution

Example 1: Reduction of Cr2O72- to Cr3+ in acidic medium

STEP 1: Balance the number of ATOMS of the substance being reduced or oxidised, excluding OXYGEN
and HYDROGEN.
E.g.: Cr2O72-  Cr3+
Cr atom is balanced by writing a 2 in front of Cr3+:
Cr2O72-  2Cr3+
STEP 2: Balance the number of OXYGEN by adding the correct number of H2O on the appropriate side.
Cr2O72-  2Cr3+
7 moles of H2O are needed on the right-hand side to balance the 7 OXYGEN atoms in Cr2O72-, so
the equation becomes:
Cr2O72-  2Cr3+ + 7H2O
STEP 3: Balance the number of HYDROGEN by adding the correct number of H+

on the appropriate side. By doing so, this is also representative of an acidic medium in which the
reaction takes place.
e.g. Cr2O72-  2Cr3+ + 7H2O
14 moles of H+ are needed on the left-hand side to balance the 14 HYDROGEN atoms, so the
equation becomes:

Cr2O72- + 14H+  2Cr3+ + 7H2O

STEP 4: Balance the CHARGE by adding the correct number of electrons, e-

on the side which is more positive.

e.g. Cr2O72- + 14H+  2Cr3+ + 7H2O

Total charges on left-hand side = -2 + 14 = +12

Total charges on right-hand side = 2(+3) = +6

So in order to balance the charges, 6 moles of ELECTRONS are added to the left-hand side, so
the equation becomes:

Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O

This is the balanced half-equation for the reduction of Cr2O72- in acidic medium.

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Example 2: Write a balanced equation for the oxidation of Fe2+ by Cl2:

Fe2+ + Cl2 → Fe3+ + Cl-

STEP 1: Write half-equations which indicate the species undergoing oxidation and reduction.
Balance all atoms.

　Fe2+ → Fe3+ Cl2 → 2Cl-

At this point, there is no need to balance the equations with H+ or H2O. STEPS 2 and 3 are not required. In
order to balance the charges, we proceed from STEP 4 onwards.

STEP 4: Balance the charges by adding electrons on the side which is more positive.

Oxidation: Fe2+ → Fe3+ + e

Reduction: Cl2 + 2e → 2Cl-

In order to have the balanced redox equations,

STEP 5: If necessary, multiply one or both half-equations with a suitable integer such that when the
half-equations are added together, the number of electrons are cancelled.

(Fe2+ → Fe3+ + e) x2

2Fe2+ → 2Fe3+ + 2e ----(1)

Cl2 + 2e → 2Cl- ----(2)

STEP 6: Add the two half-equations.

Net / overall redox equation: (1) + (2)

2Fe2+ + Cl2 → 2Fe3+ + 2Cl-

STEP 7: Check that mass and charge are balanced, with no

electrons left in overall balanced equation.

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Example 3: Write a balanced equation for the reaction of Cr2O72- with Fe2+ in acid solution

Cr2O72- + Fe2+ Cr3+ + Fe3+

STEP 1: Write half-equations which indicate the species undergoing oxidation and reduction.
Balance all atoms except O and H.

Reduction: Cr2O72- → 2Cr3+

Oxidation: Fe2+ → Fe3+

STEP 2: Balance O by adding H2O on the appropriate side.

Reduction: Cr2O72- → 2Cr3+ + 7H2O

STEP 3: Balance H by adding H+ on the appropriate side.

Reduction: Cr2O72- + 14H+ → 2Cr3+ + 7H2O

STEP 4: Balance the charges by adding electrons on the side which is more positive.

Reduction: Cr2O72- + 14H+ + 6e → 2Cr3+ + 7H2O

Oxidation: Fe2+ → Fe3+ + e

STEP 5: If necessary, multiply one or both half-equations with a suitable integer such that when the
half-equations are added together, the electrons are cancelled.

(Fe2+ → Fe3+ + e) x6

6Fe2+ → 6Fe3+ + 6e ----(1)

Cr2O72- + 14H+ + 6e → 2Cr3+ + 7H2O ----(2)

STEP 6: Add the two half-equations and eliminate any common species to obtain the overall
balanced equation.

Net / overall redox equation: (1) + (2)

Cr2O72- + 14H+ + 6Fe2+ → 2Cr3+ + 7H2O + 6Fe3+

STEP 7: Check that mass and charge are balanced, with no electrons left in overall balanced
equation.

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2. In basic solution

E.g. SO2 + Sn2+ → Sn + SO42-

Follow STEP 1-3 in balancing for acidic medium

STEPS 1-3

Oxidation Reduction

SO2 → SO42- Sn2+ → Sn

SO2 + 2H2O → SO42-

SO2 + 2H2O → SO42- + 4H+

STEP 3(A): Add equal number of OH- on both sides according to the number of H+ present.

SO2 + 2H2O + 4OH- → SO42- + 4H+ + 4OH- Sn2+ → Sn

STEP 3(B): On the side containing both H+ and OH-, simplify them to H2O and eliminate any common
species appearing on both sides of the half equation.

SO2 + 2H2O + 4OH- → SO42- + 4H2O Sn2+ → Sn

SO2 + 4OH- → SO42- + 2H2O Sn2+ → Sn

STEP 4: Balance the charges by adding electrons on the side which is more positive.

SO2 + 4OH- → SO42- + 2H2O + 2e Sn2+ + 2e → Sn

STEP 5: If necessary, multiply one or both half-equations with a suitable integer such that when
the half-equations are added together, the electrons are cancelled.

Net Equation:
Sn2+ + SO2 + 4OH- → SO42- + Sn + 2H2O

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Summary of steps in balancing redox equation:

1. Acidic medium:

1 Write the overall unbalanced equation and assign oxidation numbers to all the atoms.
2 Construct the unbalanced oxidation and reduction half-equations.
3 Balance the element reduced or oxidized in each half-equation.
4 Balance oxygen atoms by adding H2O molecules.
5 Balance hydrogen atoms by adding H+ ions.
6 Balance overall charges by adding e- either as ‘reactant’ or ‘product.
7 Equalise the total number of e- gained or lost by multiplying the balanced half-equations by
appropriate integers.
8 Add the 2 balanced half-equations and eliminate any common terms to obtain the overall balanced
equation (with no e-).

2. Basic medium:

1
2
3
Use steps 1-6 to get balanced half-equations in acidic medium.
4
5
6
7 “Neutralise” the H+ ions by adding the required number of OH- ions to both sides of a half-equation.
8 Combine the H+ and OH- ions on the same side of the equation to form H2O
9 Re-balance the half equation by eliminating any common terms, such as H2O
1 Equalise the total number of e- gained or lost by multiplying the balanced half-equations by
0 appropriate integers.
1 Add the 2 balanced half-equations and eliminate any common terms to obtain the overall balanced
1 equation (with no e-)

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Exercise 3:
Complete and balance the following equations by the method of half-reactions:
1. I2 + S2O32-  I- + S4O62-
I2 + 2e  2I- -------------(1)
2S2O32-  S4O62- + 2e ------------- (2)
(1) + (2): I2 + 2S2O32-  2I- + S4O62-
2. MnO4- + Fe2+  Mn2+ + Fe3+ (acidic solution)

MnO4- + 8H+ + 5e  Mn2+ + 4H2O -------------(1)

Fe2+  Fe3+ + e -------------(2)
(1) + (2) x 5:
MnO4- + 8H+ + 5Fe2+  Mn2+ + 4H2O + 5Fe3+
3. MnO4- + C2O42-  Mn2+ + CO2 (acidic solution)

MnO4- + 8H+ + 5e  Mn2+ + 4H2O -------------(1)

C2O42-  2CO2 + 2e -------------(2)
(1) x 2 + (2) x 5:
2MnO4- + 16H+ + 5C2O42-  2Mn2+ + 8H2O + 10CO2
4. CN- + MnO4-  CNO- + MnO2 (basic solution)

CN- + 2OH- → CNO- + H2O + 2e ----- [1]

MnO4- + 2H2O + 3e → MnO2 + 4OH- ----[2]
[1] X 3 + [2] X 2
3CN- + 2MnO4- + H2O → 3CNO- + 2MnO2 + 2OH-
5. I2  IO3- + I- (basic solution)
I2 + 12OH-  2IO3- + 6H2O + 10e ---- [1]
I2 + 2e  2I- ---- [2]
[1] + [2] x 5:
6I2 + 12OH-  2IO3- + 6H2O + 10I-
3I2 + 6OH-  IO3- + 3H2O + 5I-

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4. REDOX TITRATIONS
- A redox titration is a type of titration based on a redox reaction (this concept is similar to acid/base
titration) that involves the transfer of electrons from a reducing agent (electron donor) to an oxidising
agent (electron acceptor).
- A typical example may have a measured volume of unknown concentration of a species in the
conical flask (analyte). This is then titrated against another species from the burette (titrant) till a
colour change is observed.
- The change in colour is an indication of the end point and an indicator may not be needed.
- From the volumes of the two solutions and the stoichiometric mole ratio in the equation, the
concentration of the analyte can be found.
Important half-equations to take note:

Reduction Reactions Oxidation Reactions

MnO4- + 8H+ + 5e  Mn2+ + 4H2O C2O42-  2CO2 + 2e

Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O 2S2O32-  S4O62- + 2e

I2 + 2e  2I- 2I-  I2 + 2e
Fe3+ + e  Fe2+ Fe2+  Fe3+ + e
H2O2 + 2H+ +2e  2H2O H2O2  O2 + 2H+ +2e

The following types of redox titration will be discussed:

1) Potassium manganate (VII)

2) Potassium dichromate (VI)
3) Iodine-thiosulfate titrations

4.1 Involving Potassium Manganate (VII) as an Oxidising Agent

 Acidified KMnO4 is a strong oxidising agent commonly used in analysing reducing agents, such
as Fe2+, I-, C2O42- and H2O2.
 The titration is carried out in the presence of dilute sulfuric acid which provides the acidic
medium
 (HCl is not used for such titrations as the Cl- can be oxidised by the acidified KMnO4 to Cl2;
HNO3 is also not used as it is an oxidising agent).
 In acidic medium, the manganate (VII) ion is reduced as follows:
MnO4- + 8H+ + 5e  Mn2+ + 4H2O

 Sufficient acid must be added and the titration is done slowly with constant swirling to prevent
the incomplete reduction of MnO4- to the brown MnO2.

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 In neutral or alkaline medium, the manganate (VII) ion is reduced as follows:

MnO4- + 4H+ + 3e  MnO2 + 2H2O

MnO2 is a brown/black solid. Hence, there is a change from purple MnO4- to brown/black.
 The end-point is reached when the purple KMnO4 is reduced to the pale pink Mn2+. The sudden
change from purple MnO4- ions to pale pink Mn2+ ions at the end-point means that no indicator
is needed. Hence KMnO4 is the preferred oxidising agent in redox titrations.
 When using KMnO4 for volumetric analysis, it is often difficult to read the meniscus of the
solution in a burette. It is therefore recommended that the surface of the solution be used as the
reference point in these titrations.

Some common redox titrations involving acidified potassium manganate (VII)

1. Reaction between manganate (VII) and iron (II)

MnO4-(aq) + 8H+(aq) + 5Fe2+(aq)  Mn2+(aq) + 4H2O(l) + 5Fe3+(aq)
Hence the mole ratio is:
1 mole MnO4- ≡ 5 moles Fe2+
Colour change at end point is from green (due to Fe2+ in the conical flask) to pale orangy-pink.

Mn2+ is the product of MnO4- in acidic medium, not MnO2.

Do not use this equation:

MnO4- + 4H+ + 3e  MnO2 + 2H2O

2. Reaction between manganate (VII) and ethanedioate ions

2MnO4-(aq) + 16H+(aq) + 5C2O42-(aq)  2Mn2+(aq) + 8H2O(l) + 10CO2(g)
Hence the mole ratio is:
2 moles MnO4- ≡ 5 moles C2O42-
Colour change at end point is from colourless to pale pink.

3. Reaction between manganate (VII) and H2O2

2MnO4-(aq) + 6H+(aq) + 5H2O2(aq)  2Mn2+(aq) + 8H2O(l) + 5O2(g)
Hence the mole ratio is:
2 moles MnO4- ≡ 5 moles H2O2
Colour change at end point is from colourless to pale pink.

Exercise 4:
25.0 cm3 of sodium nitrite solution require 25.20 cm3 of 0.0250 mol dm-3 acidified KMnO4 solution for

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oxidation. What is the concentration of the sodium nitrite solution in g dm-3? [Hint: NO2- is oxidised to NO3-
]

Solution:
MnO4- + 8H+ + 5e  Mn2+ + 4H2O -----------[1]
NO2- + H2O  NO3- + 2H+ + 2e -----------[2]
[1] x 2 + [2] x 5:
2MnO4- + 16H+ + 5NO2- + 5H2O  2Mn2+ + 8H2O + 5NO3- + 10H+
2MnO4- + 6H+ + 5NO2-  2Mn2+ + 3H2O + 5NO3-
 2 MnO4-  5 NO2-

No of moles of MnO4- = 0.0250 x (25.20/1000) = 6.300 x 10-4 mol

No of moles of NO2- = 5/2 x 6.300 x 10-4 = 1.575 x 10-3 = mole of NaNO2
Concentration of NaNO2 in mol/dm3 = 1.575 x 10-3 = 0.06300 mol dm-3
25.0/1000
Mr(NaNO2) = 69.0
Concentration of NaNO2 in g/dm3 = 0.06300 x 69.0 = 4.35 g dm-3

4.2 Involving Potassium Dichromate(VI) as an Oxidising Agent

- Acidified potassium dichromate(VI) is also used as an oxidising agent to analyse reducing

agents. It is a less powerful oxidising agent than potassium manganate(VII) and does not
oxidise Cl-. Thus it can be used to analyse reducing agents in the presence of chloride ions.
- In acidic medium, the dichromate (VI) ion is reduced as follows:
Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O

- Unlike potassium manganate(VII), potassium dichromate(VI) is not self-indicating. The

orange Cr2O72- is reduced to the green Cr3+ ions and it is practically impossible to judge the end-
point from the colour change since the green predominates long before the reduction is
complete. Thus an indicator is necessary.
- Three common colourless indicators used in dichromate titrations are:
i) N-phenylanthranilic acid. Solution changes from green to reddish violet at end point.

ii) Diphenylamine in phosphoric acid. Solution changes from green to blue violet at end
point.

iii) Barium or Sodium diphenylamine p-sulfonate (green to blue-violet)

Common redox titration involving acidified potassium dichromate(VI)

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H2 Chemistry Notes

Reaction between dichromate(VI) and ethanedioate ions

Cr2O72-(aq) + 14H+(aq) + 3C2O42-(aq)  2Cr3+(aq) + 7H2O(l) + 6CO2(g)

Hence the mole ratio is:

1 mole Cr2O72- ≡ 3 moles C2O42-

Exercise 5:
12.0g of iron (II) ammonium sulfate crystals were made up to 250 cm3 with aqueous sulfuric acid. 25.0
cm3 of this solution required 25.50 cm3 of 0.0200 mol dm-3
K2Cr2O7 (aq) for oxidation. Find the value of x in the formula of the salt, FeSO4.(NH4)2SO4.xH2O.

Solution: Cr2O72- + 14H+ + 6e  2Cr3+ + 7H2O ----- [1]

Fe2+  Fe3+ + e ----- [2]
[1] + [2] x 6:
Cr2O72- + 14H+ + 6Fe2+  2Cr3+ + 7H2O + 6Fe3+
 1 mole Cr2O72-  6 moles Fe2+

No of moles of Cr2O72- = 25.50 / 1000 x 0.0200 = 5.100 x 10-4 mol

No of moles of Fe2+ reacted with Cr2O72- = 5.100 x 10-4 x 6 = 3.060 x 10-3 mol
No of moles of Fe2+ in 250 cm3 = 3.060 x 10-3 x 250 / 25 = 3.060 x 10-2 mol
No of moles of Fe2+ in 250 cm3 = No of moles of FeSO4.(NH4)2SO4.xH2O
 Mr of FeSO4.(NH4)2SO4.xH2O = 12.0 / 3.060 x 10-2 = 392
Mr of salt = 56 + 32 + 4(16) + 2(14+4) + 32 + 4(16) + 18x = 392
x=6

Comparison between MnO4- and Cr2O72- as oxidising agents

MnO4- Cr2O72-
Only sulfuric acid can be used to provide Both sulfuric acid and hydrochloric acid
the acidic medium can be used to provide the acidic medium
Stronger O.A. [E0 = +1.52 V] Weaker O.A. [E0 = +1.33 V]

Can oxidise chloride to chlorine Cannot oxidise chloride to chlorine

No indicator is required in titrations An indicator is required in titrations.
Cannot be obtained in highly pure state Can be obtained in highly pure state
4.3 Iodine and Thiosulfate Titrations (iodometric titrations)

- Na2S2O3 (reducing agent) reduces iodine to iodide ions and itself is being oxidised in the
process to form sodium tetrathionate, Na2S4O6.

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Important Equation:

2S2O32-(aq) + I2(aq)  S4O62-(aq) + 2 I-(aq)

colourless red-brown colourless colourless

- The above reaction is used for the estimation of iodine or for substances which will liberate
iodine from potassium iodide. Most iodometric titrations involve two steps:
1) A substance (e.g. KMnO4) is normally added to potassium iodide solution to liberate iodine.
- [O]
I  I2

2) The liberated iodine is then estimated using standard thiosulfate solution.

- When the brown colour of iodine fades to pale yellow as the end-point approaches, a little
starch solution is added. This gives an intense blue colour of iodine-starch complex. At the
end-point, the blue colour vanishes. The same amount of starch should be used in each titration.

Additional Information
The formation of the blue-black solution is usually attributed to the formation of a
starch-iodine complex.

Starch solution is never added at the beginning of the titration as under high I2

concentration, I2 molecules tend to be trapped in the spiral starch molecules even at the
end-point, thus leading to inaccurate results.

- When left aside, the titrated solution may slowly become blue again. This should be ignored, as
it is due to atmospheric oxidation of the excess iodide in the reaction mixture to iodine.

Exercise 6:

In a standardisation of Na2S2O3 solution, 25.0 cm3 of 0.0204 mol dm-3 KMnO4 was added to an excess of
acidified KI solution. The iodine liberated required 24.40 cm3 of sodium thiosulfate for reduction.
Calculate the concentration of Na2S2O3 in mol dm-3.

Solution:
MnO4- + 8H+ + 5e  Mn2+ + 4H2O ----- [1]
-
2I  I2 + 2e ----- [2]
[1] x 2 + [2] x 5:
2MnO4- + 16H+ + 10I-  2Mn2+ + 8H2O + 5I2 ----- [3]

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H2 Chemistry Notes

2S2O32- + I2  S4O62- + 2I- ----- [4]

Method 1 (no of moles of I2 formed is calculated):

No of moles of KMnO4 used = 25.0/1000 x 0.0204 = 5.100 x 10-4 mol
Since KMnO4 is the limiting reagent,
No of moles of I2 liberated = 5/2 x 5.100 x 10-4 = 1.275 x 10-3 mol
No of moles of S2O32- reacted = 2 x 1.275 x 10-3 = 2.550 x 10-3 mol
Concentration of Na2S2O3 = 2.550 x 10-3 ÷ 24.40/1000 = 0.105 mol dm-3
OR
Method 2 (the “middleman”, no of moles of I2, is not calculated):
From equations [3] and [4]: 2 moles MnO4-  5 moles I2  10 moles S2O32-

No of moles of KMnO4 used = 25.0/1000 x 0.0204 = 5.100 x 10-4 mol

No of moles of S2O32- reacted = 10/2 x 5.100 x 10-4 = 2.550 x 10-3 mol
Concentration of Na2S2O3 = 2.550 x 10-3 ÷ 24.40/1000 = 0.105 mol dm-3

Exercise 7:

1.00 g of potassium iodate(V) were made up to 250 cm3 of aqueous solution. 25.0 cm3 of it were added to
excess potassium iodide solution and then acidified with sulfuric acid. The liberated iodine required 30.00
cm3 of aqueous sodium thiosulfate for reduction. What is the mass of thiosulfate ions in 1 dm3 of the
solution?
[Given: IO3- + 5I- + 6H+  3I2 + 3H2O]

Solution:
IO3- + 5I- + 6H+  3I2 + 3H2O
2S2O32- + I2  S4O62- + 2I-
No of moles of KIO3 in 250 cm3 = 1 / (39.1 + 127.0 + 3 x 16.0) = 4.671 x 10-3 mol
No of moles of IO3- in 25.0 cm3 = 25 / 250 x 4.671 x 10-3 = 4.671 x 10-4 mol

1 mole IO3- ≡ 3 moles I2 ≡ 6 moles S2O32-

No of moles of S2O32- in 30.00 cm3 = 4.671 x 10-4 x 6 = 2.802 x 10-3 mol
No of moles of S2O32- in 1 dm3 = 2.802 x 10-3 ÷ (30/1000) = 0.09341 mol
Mass of S2O32- in 1 dm3 solution = 0.09341 x [2(32.1) + 3(16.0)] = 10.5 g
Exercise 8:
Calculate the percentage purity of an impure sample of sodium thiosulfate from the following data. A
0.2368 g sample of the sodium thiosulfate was added to 25.0 cm3 of 0.0400 mol dm-3 iodine solution. The
excess of iodine that remained after reaction needed 27.80 cm3 of 0.0400 mol dm-3 thiosulfate solution in

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a titration.

Solution:
2S2O32- + I2  S4O62- + 2I- (+ unreacted I2)
impure in excess
2S2O 3
2-
+ I2 (unreacted)  S4O62- + 2I-

No of moles of S2O32- = 0.04 x 27.80/1000 = 1.112 x 10-3 mol

No of moles of unreacted I2 = ½ x 1.112 x 10-3 = 5.560 x 10-4 mol
No of moles of I2 present initially = 0.04 x 25.0/1000 = 1.000 x 10-3 mol
No of moles of reacted I2 = Moles of I2 initially  Moles of unreacted I2
= 1.000 x 10-3  5.560 x 10-4
= 4.440 x 10-4 mol

No of moles of S2O32- reacted = 2 x no of moles of reacted I2

= 2 x 4.440 x 10-4
= 8.880 x 10-4 mol
= No of moles of Na2S2O3

Mass of Na2S2O3 = 8.880 x 10-4 x [2(23.0) + 2(32.1) + 3(16.0)] = 0.1405 g

% purity = 0.1405 / 0.2368 x 100% = 59.3%

Addition Information
Photochromic glass darkens on strong exposure to strong light and becomes clearer when the
light is not so strong. The glass contains small particles of silver chloride and copper(I) chloride.

When the light is strong, Ag+ ions oxidise Cu+ to Cu2+:

Ag+ + Cu+  Ag + Cu2+

The silver produced reflects light from the glass and cuts out transmission (glare) to the eye.

In low intensity, copper(II) ions oxidise Ag back to Ag + ions and the glass becomes transparent
again.

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