106

chapter 7:
Redox reactions
Learning outcomes
You should be able to:
calculate oxidation numbers of elements in use changes in oxidation numbers to help balance
compounds and ions chemical equations.
describe and explain redox processes in terms of
electron transfer and changes in oxidation number
 Chapter 7: Redox reactions

Introduction
Some types of reactions can cost a lot of money due
to the damage they cause. Rusting is an oxidation
reaction that destroys about 20% of iron and steel
every year. Rust is hydrated iron(III) oxide. This forms
when iron reacts with oxygen in the presence of water.
Another costly example of oxidation is the reaction
between hydrogen and oxygen that is used to propel
some types of rockets into space. In this reaction, the
hydrogen is oxidised but the oxygen is also reduced.
In fact, oxidation and reduction always take place
together, in what we call redox reactions.

Figure 7.1 A redox reaction is taking place when the fuel in

the Space Shuttles rockets burns.

What is a redox reaction?
A simple definition of oxidation is gain of oxygen by
an element. For example, when magnesium reacts with
oxygen, the magnesium combines with oxygen to form
magnesium oxide. Magnesium has been oxidised.
2Mg(s) + O2(g) 2MgO(s) chemical reaction:
A simple definition of reduction is loss of oxygen. When
copper(II) oxide reacts with hydrogen, this is the equation
for the reaction:
CuO(s) + H2(g) Cu(s) + H2O(l)
107
We can also define reduction as addition of hydrogen to
a compound and oxidation as removal of hydrogen from
a compound. This is often seen in the reaction of organic
compounds (see page 237).
There are two other ways of finding out whether or
not a substance has been oxidised or reduced during a
electron transfer
changes in oxidation number.
Question

Copper(II) oxide loses its oxygen. Copper(II) oxide has 1 a In each of the following equations, state which
been reduced. reactant has been oxidised:
But if we look carefully at the copper oxide/hydrogen i PbO + H2 Pb + H2O
equation, we can see that oxidation is also taking place. ii CO + Ag2O 2Ag + CO2
The hydrogen is gaining oxygen to form water. The iii 2Mg + CO2 2MgO + C
hydrogen has been oxidised. We can see that reduction
b In each of the following equations, state which
and oxidation have taken place together. reactant has been reduced:
Oxidation and reduction always take place together.
i 5CO + I2O2 5CO2 + I2
We call the reactions in which this happens redox
reactions. Redox reactions are very important. For ii 2H2S + SO2 3S + 2H2O
example, one redox reaction photosynthesis provides iii CH2 CH2 + H2 CH3CH3
food for the entire planet, and another one respiration
keeps you alive. both are redox reactions.
 Cambridge International AS Level Chemistry

Redox and electron transfer Each copper(II) ion gains two electrons. The copper ions
have been reduced.
Half-equations Cu2+ + 2e Cu
We can extend our definition of redox to include reactions
involving ions. Balancing half-equations
We can construct a balanced ionic equation from two half-
Oxidation Is Loss of electrons. equations by balancing the numbers of electrons lost and
Reduction Is Gain of electrons. gained and then adding the two half-equations together.
The initial letters shown in bold spell OIL RIG. This may The numbers of electrons lost and gained in a redox
help you to remember these two definitions! reaction must be equal.

worked examples
Sodium reacts with chlorine to form the ionic compound
sodium chloride. 1 Construct the balanced ionic equation for the reaction
between nickel and iron(III) ions, Fe3+, from the half-
2Na(s) + Cl2(g) 2NaCl(s) equations:
We can divide this reaction into two separate equations, Ni(s) Ni2+(aq) + 2e
one showing oxidation and the other showing reduction. Fe (aq) + e
3+ Fe2+(aq)
We call these half-equations.
When sodium reacts with chlorine: Each Ni atom loses two electrons when it is
oxidised. Each Fe3+ ion gains one electron when it is
Each sodium atom loses one electron from its outer shell. reduced.
Oxidation is loss of electrons (OIL). The sodium atoms have So two Fe3+ ions are needed to gain the two
been oxidised. electrons lost when each Ni2+ ion is formed
108 Na Na+ + e
2Fe3+(aq) + 2e 2Fe2+(aq)
This half-equation shows that sodium is oxidised. Ni(s) Ni (aq) + 2e
2+

It is also acceptable to write this half-equation as:

The balanced ionic equation is:
Na e Na+ Ni(s) + 2Fe3+(aq) Ni2+(aq) + 2Fe2+(aq)

Each chlorine atom gains one electron to complete its outer note how the electrons have cancelled out.
shell. Reduction is gain of electrons (RIG). The chlorine 2 Construct the balanced ionic equation for the reaction
atoms have been reduced. of iodide ions (I) with manganate(VII) ions (MnO4) in
the presence of hydrogen ions (H+). Use the following
Cl2 + 2e 2Cl
two half-equations to help you:
This is a half-equation showing chlorine being reduced. i 2I(aq) I2(aq) + 2e
There are two chlorine atoms in a chlorine molecule, so ii MnO4(aq) + 8H+(aq) + 5e Mn2+(aq) + 4H2O(l)
two electrons are gained.
In another example iron reacts with copper(II) ions, When two iodide ions are oxidised, they lose two
electrons. Each MnO4 ion gains five electrons when
Cu2+, in solution to form iron(II) ions, Fe2+, and copper.
it is reduced.
Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s) So we must multiply equation i by 5 and equation
ii by 2 to balance the number of electrons:
Each iron atom loses two electrons to form an Fe2+ ion. The 10I(aq) 5I2(aq) + 10e
iron atoms have been oxidised.
2MnO4(aq) + 16H+(aq) + 10e 2Mn2+(aq)+ 8H2O(l)
Fe Fe2+ + 2e
The balanced ionic equation is:
It is also acceptable to write this half-equation as: 2MnO4(aq) + 10I(aq) + 16H+(aq)

Fe 2e Fe2+ 2Mn2+(aq) + 5I2(aq) + 8H2O


Question
2 a Write two half-equations for the following
reactions. For each half-equation state whether
oxidation or reduction is occurring.
i Cl2 + 2I I2 + 2Cl
ii 2Mg + O2 2MgO
iii 4Fe + 3O2
 2Fe2O3
b Zinc metal reacts with IO3 ions in acidic solution.
Construct a balanced ionic equation for this
reaction, using the two half-equations below:
2IO3 + 12H+ + 10e I2 + 6H2O
Zn Zn2+ + 2e
Oxidation numbers
What are oxidation numbers?
We can extend our definition of redox even further to include
oxidation and reduction in reactions involving covalent
compounds. We do this by using oxidation numbers
(oxidation numbers are also called oxidation states). An
oxidation number is a number given to each atom or ion in a
compound that shows us its degree of oxidation. Oxidation
numbers can be positive, negative or zero. The + or sign must
always be included. Higher positive oxidation numbers mean
that an atom or ion is more oxidised. Higher negative oxidation
numbers mean that an atom or ion is more reduced.
Oxidation number rules
We can deduce the oxidation number of any atom or
ion by using oxidation number rules. It is important to
note that an oxidation number refers to a single atom in
a compound.
1 The oxidation number of any uncombined element is
zero. For example, the oxidation number of each atom
in S8, Cl2 and Zn is zero.
2 In compounds many atoms or ions have fixed
oxidation numbers
Group 1 elements are always +1
Group 2 elements are always +2
fluorine is always 1
hydrogen is +1 (except in metal hydrides such as
NaH, where it is 1)
oxygen is 2 (except in peroxides, where it is 1, and
in F2O, where it is +2).
3 The oxidation number of an element in a monatomic
ion is always the same as the charge. For example,
Cl is 1, Al3+ is +3.
Chapter 7: Redox reactions
4 The sum of the oxidation numbers in a compound
is zero.
5 The sum of the oxidation numbers in an ion is equal to
the charge on the ion.
6 In either a compound or an ion, the more
electronegative element is given the negative
oxidation number.
Figure 7.2 This is part of a ships hull. It is made of iron
protected by bars of magnesium metal. The magnesium
atoms (oxidation number = 0) are oxidised to Mg 2+ ions 109
(oxidation number = +2) in preference to iron atoms changing
to Fe3+. This is called sacrificial protection.
Applying the oxidation number rules
In the following examples we shall use ox. no. as an
abbreviation for oxidation number.
Compounds of a metal with a non-metal
The metal always has the positive ox. no. and the non-
metal has the negative ox. no. For example in sodium
oxide, Na2O, Na = +1 and O = 2.
If we do not know the ox. no. of one of the atoms, we
can often work it out using the invariable ox. nos. in rule 2.
For example in sodium sulfide:
ox. no. of each Na atom = +1
for two sodium atoms = +2
Na2S has no overall charge, so the total ox. no. is zero
(rule 4)
ox. no. of S = 2.
Compounds of a non-metal with a non-metal
In compounds containing two different non-metals, the
sign of the ox. no. depends on the electronegativity of each
atom (see page 157). The most electronegative element is
given the negative sign (rule 6).
 Cambridge International AS Level Chemistry

Sulfur dioxide, SO2

Redox and oxidation number
ox. no. of each O atom = 2
We can define oxidation and reduction in terms of the
for two oxygen atoms = 2 (2) = 4
oxidation number changes of particular atoms during
SO2 has no charge, so the total ox. no. is zero (rule 4)
a reaction.
ox. no. of S = +4

Iodine trichloride, ICl3 Oxidation is an increase of oxidation number.

chlorine is more electronegative than iodine, so chlorine is Reduction is a decrease in oxidation number.
and iodine is +
ox. no. of each Cl atom = 1
for three chlorine atoms = 3 (1) = 3
For example, when tin reacts with nitric acid, the
ICl3 has no charge, so the total ox. no. is zero (rule 4)
oxidation numbers of each atom of tin and nitrogen
ox. no. of I = +3 change as shown below.

Hydrazine, N2H4 reduction

nitrogen is more electronegative than hydrogen, so nitrogen
is and hydrogen is +
Sn + 4HNO3 SnO2 + 4NO2 + 2H2O
ox. no. of each H atom = +1 (rule 2) oxidation numbers 0 +5 +4 +4
for four hydrogen atoms = 4 (+1) = +4
N2H4 has no charge, so the total ox. no. is zero (rule 4)
ox. no. of two N atoms = 4 oxidation
ox. no. of each N atom = 2

Compound ions
Compound ions are ions with two or more different atoms.
110 Examples are the sulfate ion, SO42, and the nitrate ion,
NO3. We use rule 5 to work out the ox. no. that we do
not know.
Nitrate ion, NO3
ox. no. of each O atom = 2
for three oxygen atoms = 3 (2) = 6
NO3 has a charge of 1, so the total ox. no. of N and O atoms
is 1 (rule 5)
ox. no. of the nitrogen atom plus ox. no. of the three oxygen
atoms (6) = 1
ox. no. of N = +5 Figure 7.3 Copper reacts with silver nitrate to form silver and
copper(II) nitrate. The ox. no. of each copper atom has increased
by two. The ox. no. of each silver ion decreases by one.
Question
Each tin atom (Sn) has increased in ox. no. by +4: tin
3 
State the ox. no. of the bold atoms in these has been oxidised. Each nitrogen atom has decreased in
compounds or ions: ox. no. by 1: nitrogen has been reduced. The ox. no. of
e NH3
a P2O5  each oxygen atom is unchanged at 2. The ox. no. of each

b SO42 f ClO 2
hydrogen atom is unchanged at +1. Oxygen and hydrogen
c H2S g CaCO3 are neither oxidised nor reduced.
d Al2Cl6 In this reaction nitric acid is acting as an oxidising agent:
oxidising agents increase the ox. no. of another atom
an atom in the oxidising agent decreases in ox. no.
the oxidising agent is the substance which gets reduced it
gains electrons.
 Chapter 7: Redox reactions

In this reaction tin is acting as a reducing agent: Nitrate ions

reducing agents decrease the ox. no. of another atom Sodium, nitrogen and oxygen can form two different
an atom in the reducing agent increases in ox. no. compounds Na+NO2 and Na+NO3 (Figure 7.4). The ox.
the reducing agent is the substance that gets oxidised it no. of sodium is +1 and the ox. no. of oxygen is 2. So it is
loses electrons. the ox. no. of nitrogen that varies.
The ox. no. of N in the NO2 ion is +3. So NaNO2 is sodium
Question nitrate(III).
The ox. no. of N in the NO3 ion is +5. So NaNO3 is sodium
4 a Deduce the change in ox. no. for the bold atoms or nitrate(V).
ions in each of the following equations. In each
case, state whether oxidation or reduction has Note that the ox. no. comes after the ion it refers to.
taken place. Ions containing oxygen and one other element have the
i 2I + Br2 I2 + 2Br
ending -ate (but hydroxide ions, OH, are an exception to
this rule). For example, ions containing chlorine and
ii (NH4)2Cr2O7 N2 + 4H2O + Cr2O3
oxygen are chlorates and ions containing sulfur and
iii 
As2O3 + 2I2 + 2H2O As2O5 + 2H+ + 4I oxygen are sulfates.
iv 2KMnO4 + 16HCl The names of inorganic acids containing oxygen end
2MnCl2 + 2KCl + 5Cl2 + 8H2O in ic. The Roman number goes directly after the ion that
b Identify the reducing agent in each of the equations contains the oxygen and another element.
above. H3PO3 is phosphoric(III) acid because the ox. no. of
phosphorus is +3.
HClO4 is chloric(VII) acid because the ox. no. of chlorine is +7.

Naming compounds a
We sometimes use Roman numbers, in brackets, to name O 111
compounds. We use these systematic names to distinguish Na+ N
different compounds made of the same elements. For
example, there are two types of iron chloride. We show the O
difference by naming them iron(II) chloride and iron(III)
chloride. The numbers in brackets are the oxidation
numbers of the iron. b
In iron(II) chloride, the ox. no. of the iron is +2. The O O
compound contains Fe2+ ions. The formula is FeCl2. Na+ N
In iron(III) chloride, the ox. no. of the iron is +3. The
compound contains Fe3+ ions. The formula is FeCl3.
O
We can also use oxidation numbers to distinguish between
non-metal atoms in molecules and ions. Figure 7.4 a One formula unit of sodium nitrate(III) and
b one formula unit of sodium nitrate(V).
Oxides of nitrogen
There are several oxides of nitrogen, including N2O, NO Salts of the common acids are usually named without
and NO2. We distinguish between these according to the including the ox. no. of the non-metal ion. For example,
ox. no. of the nitrogen atom. (The ox. no. of oxygen is Mg(NO3)2 is magnesium nitrate not magnesium nitrate(V)
generally 2.) and K 2SO4 is potassium sulfate not potassium sulfate(VI).
The ox. no. of N in N2O is +1. So this compound is Note also that we do not state the ox. no. of the metal if it
nitrogen(I) oxide. has only one oxidation state.
The ox. no. of N in NO is +2. So this compound is
nitrogen(II) oxide.
The ox. no. of N in NO2 is +4. So this compound is
nitrogen(IV) oxide.
 Cambridge International AS Level Chemistry

Question Balancing chemical equations

5 
Give the full systematic names of the following: using oxidation numbers
e 
a Na2SO3  FeSO4 We can use oxidation numbers to balance equations
b Na2SO4 
f 
Cu2O involving redox reactions. This method is especially
g 
c Fe(NO3)2  H2SO3 useful where compound ions such as nitrate(V) or
d Fe(NO3)3 
h 
Mn2O7 manganate(VII) are involved.

worked examples
From name to formula 4 Copper(II) oxide (CuO) reacts with ammonia (NH3) to
You can work out the formula of a compound from form copper, nitrogen (N2) and water.
its name.
Step 1 Write the unbalanced equation and identify
the atoms which change in ox. no. (shown here in red).
worked example CuO + NH3 Cu + N2 + H2O
+2 2 3 +1 0 0 +1 2

3 Each formula unit of sodium chlorate(V) contains Step 2 Deduce the ox. no. changes.
one sodium ion. What is the formula of sodium
chlorate(V)? ox. no. change = +3

We know that:
sodium has an ox. no. of +1
CuO + NH3 Cu + N2 + H2O
oxygen has an ox. no. of 2 +2 3 0 0
the ox. no. of chlorine is +5
112
the chlorate(V) ion has a charge of 1 (to balance
the 1+ charge of the sodium). ox. no. change = 2
We can work out the formula of the chlorate(V) ion
from the oxidation numbers of oxygen and chlorine Step 3 Balance the ox. no. changes.
(let n be the number of oxygen atoms):
ox. no. change = 2 (+3) = +6
ox. no.(Cl) + ox. no.(O) = 1
+5 n (2) = 1
n =3 3CuO + 2NH3 3Cu + N2 + H2O
and sodium chlorate(V) 3 (+2) 2 (3) 0 0
So the chlorate(V) ion is ClO3
is NaClO3.

ox. no. change = 3 (2) = 6

Question The change in ox. nos. are 2 for the copper and +3
for the nitrogen. To balance the ox. no. changes, we
6 
Give the formulae of: need to multiply the copper by 3 and the nitrogen in
the ammonia by 2. The total ox. no. changes are then
a sodium chlorate(I)
balanced (6 and +6). Note that we do not multiply
b iron(III) oxide the N2 by 2 because there are already two atoms of
c potassium nitrate(III) nitrogen present. Once these ratios have been fixed
d phosphorus(III) chloride. you must not change them.
Step 4 Balance the atoms.
There are six hydrogen atoms in the 2NH3 on the left.
These are balanced with six on the right (as 3H2O). This
also balances the number of oxygen atoms. The final
equation is
3CuO + 2NH3 3Cu + N2 + 3H2O
 Chapter 7: Redox reactions

worked examples (continued) Question

5 Manganate(VII) ions (MnO4) react with Fe2+ ions in 7 

Use the oxidation number method to balance these
the presence of acid (H+) to form Mn2+ ions, Fe3+ ions equations.
and water. a H2SO4 + HI S + I2 + H2O
Step 1 Write the unbalanced equation and identify b HBr + H2SO4 Br2 + SO2 + H2O
the atoms that change in ox. no. c V3+ + I VO2+ + I + H+
2 + H2O
MnO4 + Fe2+ + H+ Mn2+ + Fe3+ + H2O
+7 2 +2 +1 +2 +3 +1 2

Step 2 Deduce the ox. no. changes.

ox. no. change = 5
Summary
Redox reactions can be explained in terms of:

MnO4 + Fe2+ + H+ Mn2+ + Fe3+ + H2O
increase in oxidation number (oxidation
+7 +2 +2 +3 state), which is oxidation
decrease in oxidation number, which is
reduction.
ox. no. change = +1
Oxidation numbers can be used to balance
Step 3 Balance the ox. no. changes. equations.
ox. no. change = 1 (5) = 5 Redox reactions can be explained in terms
of electron loss (oxidation) or electron gain

MnO4 + 5Fe2+ + H+ Mn2+ + 5Fe3+ + H2O (reduction).
+7 +2 +2 +3

113
ox. no. change = 5 (+1) = +5

Step 4 Balance the charges.

Initially ignore the hydrogen ions, as these will be used
to balance the charges.
The total charge on the other reactants is:
(1)(from MnO4) + (5 2+)(from 5Fe2+) = 9+
The total charge on the products is:
(2+)(from Mn2+) + (5 3+)(from 5Fe3+) = 17+
To balance the charges we need 8 H+ ions on
the left.
MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + H2O
Step 5 Balance the hydrogen atoms in the water.
MnO4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O
 cambridge International AS Level chemistry

End-of-chapter questions
1 In the industrial production of nitric acid the following changes take place to the nitrogen.
stage 1 stage 2 stage 3 stage 4
N2 NH3 NO NO2 HNO3

a Give the oxidation number of the nitrogen atom in each molecule. [5]
b For each stage, state whether oxidation or reduction has taken place. In each case explain your answer. [2]
c Give the full systematic name for NO2. [1]
d Nitric acid, HNO3, reacts with red phosphorus.
P + 5HNO3 H3PO4 + 5NO2 + H2O
By referring to oxidation number changes, explain why this is a redox reaction. [5]
e Explain why nitric acid can be described as an oxidising agent in this reaction. [1]
Total = 14

2 Calcium reacts with cold water to form calcium hydroxide, Ca(OH)2, and hydrogen, H2.
a State the oxidation number of calcium in:
i calcium metal [1]
ii calcium hydroxide. [1]
b State the oxidation number of hydrogen in:
i water [1]
ii hydrogen gas. [1]
114 c Write two half-equations for the reaction between water and calcium hydroxide to show:
i the change from calcium to calcium ions [1]
ii the change from water to hydroxide ions and hydrogen. [1]
d In which one of the half-equations in part c is a reduction occurring? Give a reason for your answer. [1]
e Write a balanced equation for the reaction of calcium with water. [1]
f Explain the role played by water in this reaction. [1]
Total = 9

3 The unbalanced equation for the reaction of sulfur dioxide with bromine is shown below.
SO2 + Br2 + H2O SO42 + Br + H+

a State the oxidation number of sulfur in:

i SO2 [1]
ii SO42 [1]
b State the oxidation number of bromine in:
i Br2 [1]
ii Br [1]
c Identify the reducing agent in this reaction. Give a reason for your answer. [1]
d State the change in oxidation number for:
i each S atom [1]
ii each bromine atom. [1]
e Construct a balanced equation for this reaction. [2]
Total = 9
 Chapter 7: Redox reactions

4 Aluminium reacts with hydrochloric acid to form aluminium chloride, AlCl3, and hydrogen. This is a redox reaction.
a Explain in term of electrons, what is meant by a redox reaction. [3]
b i Write a half-equation to show aluminium changing to aluminium ions. [1]
ii Write a second half-equation to show what happens to the hydrogen ions from the acid. [1]
iii What is the change in oxidation number when a hydrogen ion turns into a hydrogen atom? [1]
c Construct a balanced ionic equation for the reaction between aluminium atoms and hydrogen ions. [1]
Total = 7
5 Iodine, I2, reacts with thiosulfate ions, S2O32 to form iodide ions, I, and tetrathionate ions, S4O62.
I2 + 2S2O32 2I + S4O62
a State the oxidation number of each sulfur atom in:
i a S2O32 ion [1]
ii a S4O62 ion. [1]
b Explain in terms of electron transfer why the conversion of iodine to iodide ions is a reduction reaction. [1]
c When a salt containing iodide ions is warmed with concentrated sulfuric acid and MnO2, iodine is evolved.
2I + MnO2 + 6H+ + 2SO42 I2 + Mn2+ + 2HSO4 + 2H2O

i State the systematic name for MnO2. [1]

ii What is the oxidation number of S in the SO42 ion? [1]
iii Which reactant gets oxidised in this reaction? Explain your answer by using oxidation numbers. [1]
iv Which substance is the oxidising agent? Explain your answer. [1]
Total = 7 115
6 The compound KBrO3 decomposes when heated.
2KBrO3 2KBr + 3O2
a State the oxidation numbers of bromine in:
i KBrO3 [1]
ii KBr. [1]
b Explain using oxidation numbers why this reaction is a redox reaction. [3]
c State the systematic name of KBrO3. [1]
d When KBrO3 reacts with hydrazine, N2H4, nitrogen gas is evolved.
2KBrO3 + 3N2H4 2KBr + 3N2 + 6H2O

i What is the oxidation number change of the bromine atom when KBrO3 is converted to KBr? [1]
ii What is the oxidation number change for each nitrogen atom when N2H4 is converted to N2? [2]
iii Use your answers to i and ii to explain why 2 moles of KBrO3 react with 3 moles of N2H4. [3]
Total = 12