Reduction-Oxidation (Redox) Reactions
1. Simple half-equations
In inorganic chemistry, oxidation and reduction are best defined in terms of electron transfer.
Oxidation is the loss of electrons. When a species loses electrons it is said to be oxidised.
Eg. Na Na+ + e (each sodium atom loses one electron)
2I- I2 + 2e (each iodide ion loses one electron, so two in total)
Reduction is the gain of electrons. When a species gains electrons it is said to be reduced.
Eg. Cl2 + 2e 2Cl- (each chlorine atom gains one electron, so two in total)
Al3+ + 3e Al (each aluminium ion gains three electrons)
Processes which show the gain or loss of electrons by a species are known as half-equations.
They show simple oxidation or reduction processes.
2. Oxidation numbers
The oxidation number of an atom is the charge that would exist on an individual atom if
the bonding were completely ionic.
Oxidation: An increase in the oxidation state (number) of a free element or an atom in a
compound.
Reduction: A decrease in the oxidation state (number) of a free element or an atom in a
compound.
What is a redox reaction?
Half-equations consider gain and loss of electrons, but in fact electrons cannot be created or
destroyed; they can only be transferred from species to species. Gain of electrons by one species
necessarily involves loss of electrons by another. Oxidation and reduction thus always occur
simultaneously; an oxidation is always accompanied by a reduction and vice versa. Any reaction
consisting of the oxidation of one species and the reduction of another is known as a redox
reaction.
Rules for determining oxidation state of elements
1. The oxidation state of any free, uncombined element is zero e.g. N in N2, O in O2, Pb in
Pb etc
2. The oxidation state of atoms of elements in a compound in group I or II is +1 or +2
respectively. Na+, K+, H+ all have an oxidation number of +1. Mg2+, Ca2+, all have an
oxidation number of +2.
3. Hydrogen usually has an oxidation state of +1 except in ionic hydrides (compounds with
only a metals and hydrogen) then it is -1 e.g. NaH
4. The oxidation state of oxygen is usually -2, except in peroxides e,g. hydrogen peroxide,
where it is -1.
5. The oxidation state of any free halide ion or a halogen in a binary compound is -1. Cl-,
Br-, I- all have an oxidation number of -1.
6. The sum of oxidation numbers in a neutral compound is zero.
SO3; oxidation number of S = +6, oxidation number of each O = -2.
+6 + 3(-2) = 0
H2O2; oxidation number of H = +1, oxidation number of O = -1.
2(+1) + 2(-1) = 0
7. The sum of oxidation numbers in a polyatomic ion is equal to the charge of the ion.
SO42-; oxidation number of S = +6, oxidation number of O = -2.
+6 + 4(-2) = -2
3-
PO4 ; oxidation number of P = +5, oxidation number of O = -2.
(+5) + 4(-2) = -3
-
ClO ; oxidation number of Cl = +1, oxidation number of O = -2.
+1 +(-2) = -1
NB: The oxidation state of a monatomic ion is equal to the charge on the ion.
The oxidation numbers of all other atoms in their compounds can [Link] following the above
guidelines, the oxidation number of any atom in a compound or ion can be deduced.
During oxidation and reduction, the oxidation numbers of atoms change.
If an atom is oxidized, its oxidation number increases
(ie it becomes more +ve or less –ve)
If an atom is reduced, its oxidation number decreases
(ie it becomes less +ve or more –ve)
These ideas can be summarized in the following table:
Oxidation Loss of Increase in
electrons oxidation
number
Reduction Gain of Decrease in
electrons oxidation
number
How to write full balanced equations using two half equations
1. In ½ equations, electrons are present.
2. When combining two ½ equations, one must ensure the number of electrons involved are the
same for both equations.
3. This is done by multiplying one or both equations by an integer to make the number of
electrons equal in both equations.
4. When this is done, all the species in the equation would be multiplied by that integer chosen.
5. Combine the two half equations without including the electrons and you are done!
6. Remember the full equation must have the same total charge on both sides AND state
symbols!!!
Equation I has 6 electrons involved and equation II has 1 electron involved. Therefore equation
II is multiplied by 6 to have 6 electrons involved. Therefore equation II changes to:
6Fe2+ - 6e- → 6Fe3+
Combining both equations and removing the electrons would give:-
Oxidising agents and reducing agents
The species which is reduced is accepting electrons from the other species and thus causing it to
be oxidised. It is thus an oxidising agent.
H2SO4, Al3+ and Cl2 are all oxidising agents.
The species which is oxidised is donating electrons to another species and thus causing it to be
reduced. It is thus a reducing agent.
Na, O2-, I- and S2O32- are all reducing agents.
A redox reaction can thus be described as a transfer of electrons from a reducing agent to an
oxidising agent.
Eg I2 + 2S2O32- 2I- + S4O62-
Half-equations: I2 + 2e 2I- (reduction)
2S2O32- S4O62- + 2e (oxidation)
I2 is the oxidising agent; S4O62- is the reducing agent.
Disproportionation
There are many substances which readily undergo both oxidation and reduction, and which can
therefore behave as both oxidising agents and reducing agents. H2O2 and ClO- are two examples:
Eg H2O2 + 2H+ + 2e 2H2O reduction
H2O2 O2 + 2H+ + 2e oxidation
Eg ClO- + 2H+ + 2e Cl- reduction
ClO- ClO3- + 4H+ + 4e oxidation
Species such as these are capable of undergoing oxidation and reduction simultaneously.
The simultaneous oxidation and reduction of the same species is known as
disproportionation.
Disproportionation reactions are special examples of redox reactions.
Eg H2O2 + 2H+ + 2e 2H2O reduction
H2O2 O2 + 2H+ + 2e oxidation
2H2O2 2H2O + O2 disproportionation
oxidation numbers: +1 -2 0
Eg (ClO- + 2H+ + 2e Cl-) x 2 reduction
ClO- ClO3- + 4H+ + 4e oxidation
3ClO- 2Cl- + ClO3- disproportionation
oxidation numbers +1 -1 +5
