Topic 2.

3: Redox

1. Concept of Oxidation Number

• Oxidation number (O.N.) is a number assigned to an atom or ion to

describe its relative state of oxidation or reduction.
➢ O.N. can be +ve, –ve or zero. The + or – sign must always be included.
➢ Higher +ve O.N. means that an atom ion is more oxidized.
➢ Higher –ve O.N. means that an atom ion is more reduced.
➢ It is important to note that an O.N. refers to a single atom in a compound.
• Rules for assigning oxidation numbers are as follows:
1. The O.N. of an uncombined element is zero.
Example: Cl2, O.N. of Cl = ……………..
S8 , O.N. of S = ……………..
Na O.N. of Na = ……………..

2. The O.N. of a simple ion is equal to its ionic charge

Example: Na+, O.N. of Na = ……………..
Cu2+ , O.N. of Cu = ……………..
N3- O.N. of N = ……………..

3. The sum of the O.N. of all the atoms or ions in a compound is zero.

Example, in CO2, the sum of the O.N. is …………………………….

in FeCl3, the sum of the O.N. is …………………………….
4. For a ion, the sum of the ON’s equals the charge of the ion
Example, in SO2-4, the sum of the O.N. is ………………………………...

in MnO-4, the sum of the O.N. is ………………………………..

5. The O.N. of hydrogen is always +1, except in metal hydrides it is –1

Example , in HCl, the O.N. of H is ……………………………..

in NaH, the O.N. of H is ……………………….…...

6. The more electronegative element is given the negative O.N.

Example , in NCl3, the O.N. of N is …….….… and Cl is ……………..

in NF3, the O.N. of N is …………… and F is ………………

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 7. The O.N. of oxygen is always –2 except in peroxides and flourides

Example , in H2O, the O.N. of O is ……………………………..

in H2O2, the O.N. of O is ……………………….…...
in F2O, the O.N. of O is ……………………….…...

8. In compounds, many atoms or ions have fixed O.N.

Example , Group 1 elements are always +1

Group 2 elements are always +2
Fluorine is always –1

• In compounds containing two different non-metals, the sign of O.N. depends

on the electronegativity of each atom. The most electronegative atom is
given the negative sign (rule 6). So many atoms or ions do not have fixed
O.N.

Example 1 : Group 5 elements

1. Deduce the O.N. of nitrogen in the following compounds:

(a) N2 (b) N2O (c) NO (d) NO2

IUPAC
name
(e) NaNO2 (f) NaNO3 (g) Na3N

IUPAC
name

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 Example 2: Group 6 elements

2. Deduce the O.N. of sulfur in:

(a) H2S (b) S8 (c) S2O32– (d) S4O62–

(e) H2SO3 (f) S2O62– (g) H2SO4 (h) KHSO4

Example 3: Group 7 elements

3. Deduce the O.N. of chlorine in:

(a) NaCl (b) Cl2 (c) NaClO

IUPAC
name
(d) NaClO2 (e) NaClO3 (f) HClO4

IUPAC
name

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• Transition elements have variable O.N. in their compounds

Example 4 : Transition elements

4. Name the following compounds:

(a) FeBr2 (b) FeBr3 (c) Na2CrO4 (d) Na2Cr2O7

2. Oxidation and reduction as electron transfer

• The combustion of magnesium in oxygen in an oxidation reaction:

Mg(s) + ½ O2(g) ⎯→ MgO(s)
• During the reaction, electron is transferred from metal to non-metal forming
ions
-
2e

Mg + ½ O2 ⎯→ Mg2+O2-

• This reaction can be written in two processes :-

Oxidation : Mg → Mg2+ + 2e
Reduction : ½ O2 + 2e → O2-

• Definition of oxidation and reduction process is summarised in table below:

Oxidation Reduction
Addition of oxygen Removal of oxygen
Removal of hydrogen Addition of hydrogen
Loss of electron Gain of electron
Increase in O.N. Decrease in O.N.

• OIL : Oxidation Is Loss of electrons and

RIG : Reduction Is Gain of electrons.
The term OIL RIG may help you to remember these two definitions!

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3. Identifying redox reactions
• A redox reaction – is a reaction in which both oxidation and reduction occurs
together. Therefore, one species is oxidised while another is reduced.
• A oxidising agent – is an electron acceptor ; a species itself is reduced.
• A reducing agent – is an electron donor ; a species itself is oxidised

Exercise 2

1. State which element is oxidised and which is reduced, giving the relevant
changes in oxidation number.
Also identify the oxidizing agent and the reducing agent.
(a) Mg + 2 HCl → MgCl2 + H2

(b) 2 SO2 + O2 → 2 SO3

(c) Cl2 + 2 H2O → 4 HCl + O2

(d) (NH4)2Cr2O7 → Cr2O3 + N2 + 4 H2O

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2. Explain why the following reactions are not redox reaction.
(a) MgO + 2 HCl → MgCl2 + H2O

(b) BaCl2 + H2SO4 → BaSO4 + 2 HCl

4. Ionic half-equations
• In this redox reaction :-
Sn2+ + 2Fe3+ → Sn4+ + 2Fe2+ (1)

• Eq(1) can be written in two processes :-

Oxidation : Sn2+ → Sn4+ + 2e (2)
Reduction : 2Fe3+ + 2e → 2Fe2+ (3)

• Eq (2) and Eq (3) are described as ionic half-equations.

• Half equation is used to describe either the gain or loss of electrons in a
reaction
• Eq (1) is described as ionic equation.

Exercise 3

1. Write an ionic half-equation to show the:

(a) oxidation of K to K+ ion

(b) oxidation of Fe2+ ions to Fe3+ ions

(c) reduction of Cl2 to Cl- ions

(d) reduction of water to H2 and OH- ions

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5. More complex ionic half-equations

• Some oxidising agents e.g. MnO4- require the presence of acid.

• The H+ ions are on the left side of reaction to pick up the oxygen atom from
MnO4- to form Mn2+ and H2O.
• Example: MnO4- being reduced to Mn2+ in acidic solution.

Step 1 MnO4- ⎯→ Mn2+

Step 2 MnO4- ⎯→ Mn2+ + 4H2O
Step 3 MnO4- + 8H+ ⎯→ Mn2+ + 4H2O balanced in terms of atoms
Step 4 +7 +2
Step 5 MnO4- + 5e + 8H ⎯→ Mn2+ + 4H2O
- +
now balanced

Take note: In step 2, atom balance cannot be made by adding 2O2 to the right hand
side. The answer is to have H+ ion on the left-hand side

Exercise 4

1. Balance the following half-equation (remember you may need to add

H+/H2O)
(a) Cr2O72- → Cr3+

(b) NO3- → NO2-

(c) IO3- → I2

(d) SO42- → H2S

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 (e) C2O42- → CO2

(f) H2O2 → O2

6. Combining half-equations

• Half-equations can be combined to give the overall equation for a redox

reaction.
• The equations can be balanced in 3 steps….
Step 1 Multiply one/both equations so that the number of electrons is the
same
Step 2 Add the equations and cancel out the electrons on either side of the
equation
Step 3 If necessary, cancel out any other species which appear on the
both sides.

Example The reaction between MnO4- and Fe2+.

MnO4- + 5e- + 8H+ ⎯→ Mn2+ + 4H2O

( Fe2+ ⎯→ Fe3+ + e ) X5

MnO4- + 5 Fe2+ + 8H+ ⎯→ Mn2+ + 5 Fe3+ + 4H2O

Exercise 5

1. Use your half-equations from Exercise 3 and 4 to write redox equations for
the following reactions.
(a) H+/Cr2O72- + Fe2+

(b) H+/ MnO4- + Cl-

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 (c) I- + H+/IO3 -

(d) H+/Cr2O72- + C2O42-

(e) H+/ MnO4- + H2O2

2. Using half-equations, write a redox equation for the reaction of H 2SO4 with
KBr, producing S and Br2.

3. When concentrated nitric acid is added to copper metal, the copper is

oxidised to copper(II)ion and the nitric acid is reduced to nitrogen dioxide.
Derive half-equations and then write an equation for the reaction.

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7. Disproportionation
• Definition: ...........................................................................................................
............................................................................................................................
• When chlorine gas is bubbled into aqueous sodium hydroxide, a
disproportion reaction takes place.
Cl2 + 2NaOH ⎯→ NaOCl + NaCl + H2O
O.N of Cl 0 +1 -1
• Chlorine is both oxidised from 0 to +1 and reduced from 0 to -1 in the same
reaction.
Take note: To be involved in a disproportionation reaction, an element must
have at least three oxidation states – the initial one, one higher and one
lower.

Exercise 6

1. When potassium bromate(I) is heated, it decomposes according to the

equation:
3KOBr ⎯→ 2KBr + KBrO3
Explain why this is a disproportionation reaction?

2. Consider the reaction:

NaOCl + NaCl + H2SO4 ⎯→ Na2SO4 + H2O + Cl2

Explain why this is not a disproportionation reaction?

3. Is the decomposition of hydrogen peroxide a disproportionation reaction?

Explain your answer.
2H2O2 ⎯→ 2H2O + O2

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3. The propellant used in the solid rocket booster of a space shuttle is a
mixture of aluminium and compound X. Compound X contains chlorine in
an oxidation state of +7. Which of the following could be compound X?
A NH4Cl
B NH4ClO3
C NH4ClO4
D N2H5Cl

4. In black and white photographic film, light converts silver chloride into
metallic silver. After the film has been developed, the unexposed silver
chloride is removed by reaction with sodium thiosulphate to produce a
‘fixed’ negative?
AgCl + 2Na2S2O3 ⎯→ 4Na+ + Cl- + [Ag(S2O3)2]3-
What is the function of thiosulphate?
A to make the silver ions soluble
B to oxidise the silver ions
C to oxidise the silver metal
D to reduce the silver ions

6. When ammonia is converted into nitric acid on a commercial scale, the

following reactions can occur.

In which reaction does the greatest change in oxidation number of the

nitrogen occur?
reaction
A 4NH3 + 5O2 → 4NO + 6H2O
B 3NO2 + H2O → 2HNO3 + NO
C 2NO + O2 → 2NO2
D 4NH3 + 6NO → 5N2 + 6H2O

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7. A weedkiller can be prepared by heating a bleach solution.
3NaClO ⎯→ 2NaCl + NaClO3
bleach weedkiller

What are the oxidation states of chlorine in these compounds?

A -1 -1 +5
B +1 -1 +5
C +1 -1 +7
D +2 +1 +7

8. Chlorine dioxide is produced on a large scale as it is used for bleaching

paper pulp. It is made by the following reaction.

2 ClO3-(aq) + SO2(g) → 2ClO2(g) + SO42-(aq)

How do the oxidation numbers of chlorine and sulphur change in this

reaction?
reaction chlorine sulphur
A decreases by 1 increases by 1
B decreases by 1 increases by 2
C decreases by 3 increases by 1
D decreases by 3 increases by 2

10. In some early paintings, lead(II) carbonate was used as a white pigment.
In the 19th century hydrogen sulphide from burning coal reacted with this
pigment to form black lead(II) sulphide, PbS. The original colour of the
painting may be restored by carefully treating the area with dilute
hydrogen peroxide, producing lead(II) sulphate which is also white.

What is the role of the hydrogen peroxide?

A catalyst
B oxidising agent
C reducing agent
D solvent

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