Chapter 9: Redox equilibrium
9.1 Oxidation and reduction
9.1.1 Describe redox reactions through activities
1. Redox reaction can be explained in terms of:
Oxidation (Reducing agent)
Oxygen Gain oxygen (+)
Hydrogen Lost hydrogen (-)
Electron Lost electron (-)
Oxidation number Increase in oxidation number (+)
Oxidation in Terms of Gain of Oxygen
1. Oxidation is a chemical reaction in which
oxygen is added to a substance. If a
substance (element or compound) gains
oxygen during a reaction, it is said to be
oxidised.
2. When calcium burns in oxygen, the
following reaction occurs:
2Ca (s) + O2 (g)  2CaO (s)
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addition of oxygen (oxidation)
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(a) This process is known as oxidation.
(b) Calcium is oxidised to calcium oxide
because it gains oxygen in this reaction.
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Oxidation in Terms of Loss of Hydrogen
1. Oxidation can also be defined as the loss of
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hydrogen from a substance. If a substance
loses hydrogen during a reaction, it is said to
be oxidised.
2. When hydrogen sulphide gas is mixed with
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chlorine gas at room temperature, a yellow
precipitate of sulphur is formed and
hydrogen chloride gas is released.
H2S (g) + Cl2 (g)  2HCl (g) + S (s)
Loss of hydrogen (oxidation)
In this reaction, hydrogen sulphide loses
hydrogen and is oxidised to sulphur.
Reduction (Oxidising agent)
Lost oxygen (-)
Gain hydrogen (+)
Gain electron (+)
Decrease in oxidation number(-)
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Reduction in Terms of Loss of Oxygen
1. A reduction reaction is the reverse process of
an oxidation reaction. Reduction is defined as
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the loss of oxygen from a substance. If a
substance loses oxygen during a reaction, it is
said to be reduced.
2. When a mixture of zinc powder and copper
(II) oxide is heated, the following reaction
occurs.
Loss of oxygen (reduction)
Zn (s) + CuO (s)  ZnO (s) + Cu (s)
3. In this reaction, copper (II) oxide has lost its
oxygen. It is said to be reduced to metallic
copper.
Reduction in Terms of Gain of Hydrogen
1. Reduction can also be defined as the addition
of hydrogen to a substance. If a substance
gains hydrogen during a reaction, it is said to
be reduced.
2. When a mixture of hydrogen and chlorine is
exposed to sunlight, a vigorous reaction
occurs and white fumes of hydrogen chloride
are produced.
Addition of hydrogen
(reduction)
H2(g) + Cl2(g)  2HCl(g)
3. In this reaction, chlorine has gained
hydrogen. This means that chlorine has been
reduced.
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 3. When ammonia gas is passed over hot
copper (II) oxide, the following reaction
occurs.

2NH3(g) + 3CuO(s)  N2(g) + 3Cu(s) + 3H2O (l)

Oxidation
Ammonia undergoes oxidation because it
loses hydrogen. In other words, ammonia is
oxidised to nitrogen.

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Redox reactions

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1. Oxidation and reduction always take place together. A redox reaction is defined as a reaction in
which both oxidation and reduction take place simultaneously (at the same time).
2. In a redox reaction, when one substance in a reaction is oxidised, the other substance is reduced.
3. When steam is passed over heated magnesium, magnesium oxide and hydrogen are produced.

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oxidation

Mg(s) + H2O(g)  MgO(s) + H2(g)

reduction
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4. In this reaction, magnesium has gained oxygen and is oxidised. In contrast, water has lost its
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oxygen and is reduced.
Oxidising and reducing agents
1. An oxidising agent oxidises a substance. It is reduced in the redox reaction.
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2. A reducing agent reduces a substance. It is oxidised in the redox reaction.

3. The following are examples of oxidising and reducing agents:
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Oxidising agents Reducing agents

 Chlorine and bromine  Metals, such as sodium, magnesium,
 Acidified potassium manganate (VII) zinc and aluminium
 Acidified potassium dichromate (VI)  Sulphur dioxide gas and hydrogen
 sulphide gas
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Concentrated nitric acid

 Sodium sulphite and sodium
thiosulphate
 Potassium iodide

4. In a redox reaction involving A and B: if A is an oxidising agent, then B is the reducing agent and
vice versa.

Reaction Oxidising agent Reducing agent

The reaction between copper (II) Copper (II) oxide Carbon
oxide and carbon:  Copper (II) oxide  Carbon reduces
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 oxidises carbon to copper(II) oxide to
carbon dioxide. copper.
Oxidised (gain oxygen)  It is reduced to  It is oxidised to
copper. carbon dioxide.
2CuO(s) + C(s)  2Cu(s) + CO2(g)

Reduced (loss of oxygen)

The reaction between chlorine and Chlorine Hydrogen sulphide

hydrogen sulphide:  Chlorine oxidises  Hydrogen sulphide
Oxidised (loss of hydrogen) hydrogen sulphide reduces chlorine to

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to sulphur. hydrogen chloride.

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Cl2(g) + H2S(g)  2HCl(g) + S(s)  It is reduced to  It is oxidised to
hydrogen chloride. sulphur.

Reduced (gain hydrogen)

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Example 1: EE
The equation for the reaction between iron (III) oxide and carbon monoxide is shown below.

Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g)

Identify the oxidising and reducing agents in this reaction.
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Solution:

Fe2O3 is an oxidising agent because it oxidises CO to CO2 and is itself reduced to Fe.
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CO is a reducing agent because it reduces Fe2O3 to Fe and is itself oxidised to CO2.

*In many cases, oxidation or reduction reactions are accompanied by colour changes:
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(a) Br2 (brown)  Br- (colourless) …. Reduction

(b) MnO4- (purple)  Mn2+ (colourless) … reduction
(c) Cr2O72- (orange)  Cr3+ (green) …. Reduction
(d) Fe2+ (green)  Fe3+ (brown/yellow) … oxidation
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(e) 2I- (colourless)  I2 (brown) … oxidation

Oxidation Number

1. The oxidation number of an element is an arbitraty charge assigned to the element according to
a set of rules. Oxidation number is alson known as the oxidation state.

Oxidation numbers of elements in ionic Oxidation numbers of elements in covalent

compounds compounds
1. An ionic compound can contain Carbon dioxide, CO2 is a covalent

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 monatomic ions (for example, Na+ and
Cl- ions) or polyatomic ions (for
example, NH4+ or SO42- ions).
2. Foa a monatomic ion in an ionic
compound, the oxidation number is the
charge on the ion.
Magnesium oxide, MgO is an ionic
compound.
In magnesium oxide, magnesium exists as
magnesium ions, Mg2+ and oxygen exists as
oxide ions, O2-.
Thus, magnesium is said to have the
oxidation number of +2 and oxygen has
compound. However, when determining the
oxidation numbers of carbon and oxygen, you
will have to consider that this molecule exists
as ions.
 Each oxygen atom is considered as an
oxide ion (O2-) and carries a charge of -2.
So two oxide ions carry a total charge of -
4.
 As a result, each carbon ion carries a
charge of +4 so that CO2 exists as a neutral
molecule.

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the oxidation number of -2.

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 Therefore, the oxidation number of carbon
is +4 and the oxidation number of oxygen
is -2.

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Rules for Assigning Oxidation Numbers

Rule EE Examples Oxidation numbers

1. An atom or a molecule of Hydrogen, H2 0
an element in the free Oxygen, O2 0
state (not combined with Chlorine, Cl2 0
other elements) has an Sulphur, S 0
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oxidation number of Iron, Fe 0
zero. Copper, Cu 0
2. For monatomic ions, the Hydrogen ion, H+ +1
oxidation number equals Sodium ion, Na+ +1
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to the charge on the ion. Magnesium ion, Mg2+ +2

Aluminium ion, Al3+ +3
Chloride ion, Cl- -1
Oxide ion, O2- -2
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Nitride ion, N3- -3

3. The sum of oxidation Manganate (VII), MnO4- -1
numbers of a polyatomic Chromate (VI), CrO42- -2
ion is equal to the charge
Sulphate (VI), SO42- -2
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of the polyatomic ion

4. The sum of oxidation Sodium chloride, NaCl 0
numbers of a compound Carbon dioxide, CO2 0
is equal to zero. Sulphuric acid, H2SO4 0
5. Special cases
(i) All group 1 elements have Element Na in NaCl +1
the oxidation number +1 Element K in K2O +1
(ii)All group 2 elements have Element Mg in MgBr2 +2
the oxidation number +2 Element Ca in CaCo3 +2
(iii) All group 3 elements Element Al in Al2O3 +3
have the oxidation number
+3.
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 (iv) Group 17 elements Element Cl in NaCl -1
(Halogens) have the Element Br in MgBr2 -1
oxidation -1 in most of
their compounds Element Cl in KClO3 -1
(v) Oxygen, O has the Element O in Al2O3 -2
oxidation number -2 in
most of its compounds. An
Element in H2O2 -2
exception in hydrogen
peroxide, H2O2. (-1)

1. Calculating the oxidation numbers of elements, there are 4 steps:

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(i) Write down the fixed oxidation number of elements that has known.

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(ii) Multiply each oxidation number by the subscript of element in the chemical formula.
(iii) Write the mathematical equation to determine the unknown oxidation numbers.

2. Example: Calculate the oxidation of chromium, Cr in potassium dichromate (VI), K2Cr2O7.

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Solution:

(i) Write down the fixed oxidation number of elements

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K Cr O
Oxidation number +1 X -2
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(ii) Multiply each oxidation number by the subscript of element in the chemical formula.

K Cr O
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Oxidation number +1 X -2
Number of atom 2 2 7

(iii) Write the mathematical equation for the sum of oxidation numbers.
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K2Cr2O7 = 0
2[K] + 2[Cr] + 7[O] = 0
2(+1) + 2(X) + 7(-2) = 0
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(iv) Solve the mathematical equation to determine the unknown oxidation numbers.
2(+1) + 2(X) + 7(-2) = 0
2 + 2X -14 = 0
X = +6

3. Try this!
a. Calculate the oxidation number of sulphur, S in sulphuric acid, H2SO4. [Ans: +6]

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b. Calculate the oxidation number of bromine, Br in bromated (V) ion, BrO3-. [Ans: +5]

Exercise 1: Calculate the oxidation number of the following elements:

Compound Oxidation number of element

(a) SO3 X + 3(-2) =0
X = +6
(b) PbO2 X + 2(-2) = 0

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X = +4

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(c) HNO3 (+1) + X + 3(-2) = 0
X = +5
(d) PO43- X + 4(-2) = -3
X = +5
(e) KMnO4 (+1) + X + 4(-2) = 0

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X = +7
(f) V2O5 2X + 5(-2) = 0
X = +5
(g) NH4+ X + 4(+1) = +1

(h) CrO42-
X = -3
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X + 4(-2) = -2
X = +6
(i) HCO3- (+1) +X + 3(-2) = -1
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X = +4
(j) CuSO4 (+2) + X + 4(-2) = 0
X = +6
(k) OCl- (-2) + X = -1
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X = +1

Oxidation and Reduction in Terms of Changes in Oxidation Numbers

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1. The following equation shows the reaction between iron and chlorine.
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In this reaction,
(a) The iron metal is oxidised to iron (III) chloride because its oxidation number increases from
0 to +3.

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 (b) Chlorine (Cl2) is reduced to chloride ion (Cl-) because its oxidation number decreases from
0 to -1.
(c) Chlorine acts as the oxidising agent because it oxidises iron and is itself reduced.
(d) Iron acts as the reducing agent because it reduces chlorine and is itself oxidised.

2. When chlorine gas is passed into potassium bromide solution, the following reaction occurs:

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In this reaction,

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(a) Bromide ion (Br-) is oxidised to bromine because the oxidation number of bromine increases
from -1 to 0.
(b) Chlorine (Cl2) is reduced to chloride ion (Cl-) because the oxidation number of chlorine
decreases from 0 to -1.
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(c) Chlorine acts an oxidising agent and potassium bromide acts as a reducing agent.
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3. Ammonia reacts with copper (II) oxide as represented by the equation:
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In this reaction,
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(a) Ammonia is oxidised to nitrogen because the oxidation number of nitrogen increases from -3
to 0.
(b) Copper (II) oxide is reduced to copper because the oxidation number of copper decreases
from +2 to 0.
(c) Copper (II) oxide acts as an oxidising agent and ammonia acts as a reducing agent.
(d) The oxidation numbers of hydrogen and oxygen remain unchanged.

4. A reaction is not a redox reaction if the substances involved in the reaction do not undergo any
changes in oxidation numbers. For example,

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 The reaction between sodium hydroxide (NaOH) and sulphuric acid (H2SO4) is a neutralisation
reaction and not a redox reaction. As a result, the oxidation numbers of all the elements (sodium,
oxygen, hydrogen and sulphur) are the same before and after the reaction.

Oxidation and reduction always take place together. A redox reaction must have
 A substance that undergoes oxidation and acts as the reducing agent, and
 Another substance that undergoes reduction and acts as the oxidising agent.

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Oxidation and reduction in terms of Electron Transfer

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1. In terms of electron transfer,
(a) Oxidation is defined as the loss of electrons from a substance. If a substance loses electrons
during a reaction, it has been oxidised.
(b) Reduction is defined as the gain of electrons by a substance. If a substance gains electrons, it
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has been reduced.
2. During a redox reaction, transfer of electrons occurs between the reactants.
3. The reactant that loses electrons undergoes oxidation and acts as a reducing agent.
Example:
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Na (s) Na+ (aq) + e- … (1)
Oxidation
In this reaction,
(a) Sodium atoms undergo oxidation by losing electrons to form sodium ions (Na+).
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(b) Sodium acts as the reducing agent.

4. A substance that accepts electrons undergoes reduction and acts as an oxidising agent.
Example:
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Cl2 (g) + 2e- 2Cl- (aq) … (2)

Reduction
In this reaction,
(a) Each chlorine molecule (Cl2) accepts two electrons to form two chloride ions (Cl-).
(b) Chlorine acts as the oxidising agent and is itself reduced.
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5. Balancing half-equations for oxidation and reduction

Equations (1) and (2) as shown above are known as half-equations. Half-equations must be
balanced in terms of
(a) The number of atoms
(b) The number of charges
6. (a) Zinc reacts with hydrochloric acid as represented by the equation
Zn (s) + 2HCl (aq)  ZnCl2 (aq) + H2 (g)
The ionic equation for the reaction is

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(c) The transfer of electrons can be represented by the following half-equations:

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Zn (s)  Zn2+ (aq) + 2e- ….. oxidation
Reducing agent
2H+ (aq) + 2e-  H2 (g) …. Reduction
Oxidising agent

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(d) In the reaction between hydrochloric acid and zinc, zinc is oxidised to zinc chloride whereas
hydrochloric acid is reduced to hydrogen.
(e) Hydrochloric acid acts as an oxidising agent by accepting electrons and is itself reduced.
Conversely, zinc acts as the reducing agent by donating electrons and is itself oxidised.
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7. In terms of transfer of electrons, oxidising agents are electrons acceptors while reducing
agents are electron donors.
8. If a coil of copper is placed in a solution of silver nitrate, the copper slowly dissolves and the
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solution turns blue. At the same time, the copper coil becomes coated with a layer of silver
metal.
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(a) The overall equation for the reaction is:

Cu (s) + 2AgNO3 (aq)  Cu(NO3)2 (aq) + 2Ag (s)

The reaction can be represented by the ionic equation:

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 (b) In this reaction, each silver ion (Ag+) accepts one electron to form a silver atom (Ag).

Half equation:
An oxidising agent is an electron acceptor. Hence, silver ion acts as an
______________________________ in this reaction.

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(c) Conversely, each copper atom donates two electrons and are converted to copper (II) ion
(Cu2+) in the aqueous solution.

Half equation:

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Reducing agents are electron donor. Hence, copper acts as a
____________________________.

Redox reactions by the Transfer of Electrons at a distance

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1. If a solution containing an oxidising agent is separated from a solution containing a reducing agent
by an electrolyte, the redox reaction can still occur by transfer of electrons at a distance.
2.
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3. In figure 3.10, the electrons are transferred by the connecting wire in the external circuit, from a
reducing agent to an oxidising agent.
4. The electrode placed in a solution containing a reducing agent acts as the negative terminal.
The reducing agent undergoes oxidation with the loss of electrons.
5. The electrons produced will flow through the connecting wire to the electrode placed in a
solution of oxidising agent. This electrode acts as the positive terminal.
6. Sulphuric acid acts as the salt bridge. The functions of a salt bridge are
(a) To separate the oxidising agent from the reducing agent,
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 (b) To complete the electric circuit so that ions can move through it.
7. Besides dilute sulphuric acid, the following strong electrolytes can also be used as salt bridges:
(a) Sodium or potassium chloride solution
(b) Sodium or potassium nitrate solution
Laboratory 1A
Data and observation:
Solution Observation Inference
Iron (II) sulphate Iron (II) sulphate solution At the end of the reaction, iron
changes from pale green to (III) ions are present. Iron (II)
yellow. It gives blood-red ions have changed to iron (III)

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colouration with potassium ions.

Acidified potassium manganate
(VII), KMnO4
thiocyanate solution.
The purple acidified potassium
manganate (VII) solution
decolourises.
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Manganate (VII) ions that give
the solution its purple colour are
used up in the reaction.

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1. Iron (II) ions act as the reducing agent, releasing electrons to become iron (III) ions. Thus, iron
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(II) sulphate solution changes colour from pale green to yellow.

Oxidation half-equation: Fe2+ (aq)  Fe3+ (aq) + e-
(pale green) (yellow)
2. The electrons accumulate at the carbon electrode in the iron (II) sulphate solution and flow out to
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the connecting wires. This carbon electrode acts as the negative terminal.
3. The electrons then flow to the positive terminal, which is the carbon electrode in the acidified
potassium manganate (VII) solution.
4. Manganate (VII) ions acts as the oxidising agent, accepting the electrons and therefore,
undergoing reduction to become colourless manganese (II) ions.
Reduction half-equation: MnO4- (aq) + 8H+(aq) + 5e-  Mn2+ (aq) + 4H2O (l)
(purple) (colourless)
5. The overall ionic equation is as follows:
5Fe2+ (aq) + MnO4- (aq) + 8H+ (aq)  5Fe3+ (aq) + Mn2+ (aq) + 4H2O (l)

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 Exercise:

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