Redox Reactions
Oxidation numbers
Halogens
Notes
OXIDATION AND REDUCTION
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.
In simple ions, the oxidation number of the atom is the charge on the ion:
Na+, K+, H+ all have an oxidation number of +1.
Mg2+, Ca2+, Pb2+ all have an oxidation number of +2.
Cl-, Br-, I- all have an oxidation number of -1.
O2-, S2- all have an oxidation number of -2.
In molecules or compounds, the sum of the oxidation numbers on the atoms 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
SCl2; oxidation number of S = +2, oxidation number of Cl = -1.
2 + 2(-1) = 0
In complex ions, the sum of the oxidation numbers on the atoms is equal to the overall
charge on the ion.
SO42-; oxidation number of S = +6, oxidation number of O = -2.
+6 + 4(-2) = -2
PO43-; 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
In elements in their standard states, the oxidation number of each atom is zero.
In Cl2, S, Na and O2 all atoms have an oxidation number of zero.
Many atoms, such as S, N and Cl, can exist in a variety of oxidation states. The oxidation
number of these atoms can be calculated by assuming that the oxidation number of the
other atom is fixed (usually O at -2).
All group I atoms always adopt the +1 oxidation state in their compounds.
All group II atoms adopt the +2 oxidation state in their compounds.
Aluminium always adopts the +3 oxidation state in its compounds.
Fluorine always adopts the -1 oxidation state in its compounds.
Hydrogen adopts the +1 oxidation state in its compounds unless it is bonded to a metal,
Silicon or boron in which case it adopts the -1 oxidation state.
Oxygen adopts the -2 oxidation state in its compounds unless it is bonded to a group I or
group II metal or hydrogen (with which it sometimes adopts the -1 oxidation state), or
with fluorine (with which it adopts the +2 oxidation state).
The oxidation numbers of all other atoms in their compounds can vary.
By 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
3. More complex half-equations
Many oxidation and reduction processes involve complex ions or molecules and the half-
equations for these processes are more complex. In such cases, oxidation numbers are a
useful tool:
There are two ways to balance half-equations:
Method 1: (this shows you straight away whether oxidation or reduction is taking place)
Identify the atom being oxidised or reduced, and make sure there are the same
number of that atom on both sides (by balancing)
insert the number of electrons being gained or lost:
(on the left if reduction, on the right if oxidation)
No of electrons gained/lost =
change in oxidation number x number of atoms changing oxidation number
balance O atoms by adding water
balance H atoms by adding H+
Example: Write a balanced half-equation for the process SO32- SO42-
- there is one sulphur on each side, so the S is already balanced
- the oxidation number of the S is increasing from +4 to +6, so two electrons are
being lost (inserted on the right):
SO32- SO42- + 2e
- there are three O atoms on the left and four on the right, so one water is needed on
the left:
SO32- + H2O SO42- + 2e
- there are two H atoms on the left and none on the right, so two H ions are needed
on the right:
SO32- + H2O SO42- + 2H+ + 2e
The oxidation number of the S is increasing and electrons are being lost. It is an oxidation
process.
Method 2: (this does not use oxidation numbers and is easier in more complex processes)
Identify the atom being oxidised or reduced, and make sure there are the same
number of that atom on both sides (by balancing)
balance O atoms by adding water
balance H atoms by adding H+
add the necessary number of electrons to ensure the charge on both sides is the
same
Example: Write a balanced half-equation for the process H2SO4 H2S
- there is one sulphur on each side, so the S is already balanced
- there are four O atoms on the left and none on the right, so four waters are needed
on the right:
H2SO4 H2S + 4H2O
- there are two H atoms on the left and ten on the right, so eight H ions are needed
on the left:
H2SO4 + 8H+ H2S + 4H2O
- the total charge on the left is +8 and on the right is 0. So eight electrons must be
added to the left to balance the charge:
H2SO4 + 8H+ + 8e H2S + 4H2O
The oxidation number of the S is decreasing and electrons are being gained. It is a
reduction process.
4. Redox reactions
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.
A redox reaction can be derived by combining an oxidation half-equation with a
reduction half-equation in such a way that the total number of electrons gained is equal to
the total number of electrons lost.
Eg H2SO4 + 8H+ + 8e H2S + 4H2O - reduction
2I- I2 + 2e – oxidation
(the oxidation half-equation must be multiplied by 4 to equate the electrons)
8I- 4I2 + 8e
overall: H2SO4 + 8H+ + 8I- H2S + 4H2O + 4I2 - redox
Eg Al3+ + 3e Al - reduction
2O2- O2 + 4e - oxidation
(the reduction half-equation must be multiplied by 4 and the oxidation half-
equation by 3 to equate the electrons)
4Al3+ + 12e 4Al
6O2- 3O2 + 12e
overall: 4Al3+ + 6O2- 4Al + 3O2 - redox
5. 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; S2O32- is the reducing agent.
Eg H2SO4 + 8H+ + 8I- H2S + 4H2O + 4I2
Half-equations: H2SO4 + 8H+ + 8e H2S + 4H2O (reduction)
2I- I2 + 2e (oxidation)
H2SO4 is the oxidising agent, I- is the reducing agent
6. 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- + H2O) x 2 reduction
ClO- + 2H2O ClO3- + 4H+ + 4e oxidation
3ClO- 2Cl- + ClO3- disproportionation
oxidation numbers +1 -1 +5
REDOX PROPERTIES OF HALOGENS AND HALIDE IONS
i) The halogens – oxidising agents
All the halogens are oxidising agents, as they can accept electrons and get reduced:
F2(g) + 2e == 2F-(aq)
Cl2(g) + 2e == 2Cl-(aq)
Br2(l) + 2e == 2Br-(aq)
I2(aq) + 2e == 2I-(aq)
Fluorine is the best oxidising agent, followed by chlorine. Iodine is a mild oxidising
agent. The fewer the number of shells in the atom, the closer the electrons can get to the
nucleus and the less shielded the electrons are from the nucleus. The attraction of the
electrons to the nucleus is thus stronger and the atom is more likely to accept electrons.
Thus the oxidising power of the halogens decreases down a group:
Fluorine chlorine bromine iodine
Very strong Strong oxidising Fairly strong Mild oxidising
oxidising agent agent oxidising agent agent
ii) The halides – reducing agents
The halide ions are reducing agents, as they can lose electrons and get oxidised:
2F-(aq) == F2(g) + 2e
2Cl-(aq) == Cl2(g) + 2e
2Br-(aq) == Br2(aq) + 2e
2I-(aq) == I2(aq) + 2e
Iodide ions are the most reducing, followed by bromide ions. Fluoride ions have no
significant reducing properties. As the number of shells in the ion increases, there is more
shielding of the nucleus and the outer electrons become less strongly held. These
electrons are thus lost more easily and the halide ion is more readily oxidised.
Thus the reducing power of the halides increases down a group:
Fluoride chloride bromide iodide
Very poor reducing Poor reducing agent Fairly poor reducing Fairly good
agent agent reducing agent
iii) Displacement reactions between halogens and halide ions
The displacement reactions of halogens with halide ions provides a clear illustration of
the trends in oxidizing properties of the halogens and the trends in reducing properties of
the halide ions in aqueous solution:
The more reactive halogens (ie the strongest oxidising agents) will displace the more
reactive halides (ie the strongest reducing agents) from solutions of their ions:
.
Chlorine will displace bromide and iodide ions from solution.
Bromine will displace iodide ions from solution, but not chloride ions.
Iodine cannot displace either bromide or chloride ions from solution.
Cl2(g) + 2Br-(aq) 2Cl-(aq) + Br2(aq)
Orange colour will appear in solution on adding chlorine
Cl2(aq) + 2I-(aq) 2Cl-(aq) + I2(aq)
Brown colour will appear in solution on adding chlorine
Br2(aq) + 2I-(aq) 2Br-(aq) + I2(aq)
Brown colour will appear in solution after adding bromine
I2(aq) + 2Cl-(aq) 2I-(aq) + Cl2(g) will not happen
I2(aq) + 2Br-(aq) 2I-(aq) + Br2(g) will not happen
Br2(aq) + 2Cl-(aq) 2Br-(aq) + Cl2(g) will not happen
These reactions will not happen as chlorine is a stronger oxidising agent than bromine
and bromine is a stronger oxidising agent than iodine.
As size increases down a group, the ability of the atoms to accept electrons decreases and
hence their oxidising power decreases.
iv) Reaction of halide ions with concentrated sulphuric acid
The variation in reducing strength of the halides can be clearly seen in the reaction of the
sodium halides with concentrated sulphuric acid.
Concentrated sulphuric acid is a strong acid and can convert the sodium salts of the
halides into the hydrogen halides:
H2SO4(l) + NaX(s) NaHSO4(s) + HX(g)
(or H2SO4(l) + X- HSO4- + HX(g))
The halide ions are not oxidised in this reaction; in fact they are behaving as bases.
Concentrated sulphuric acid is, however, also an oxidising agent; it can be reduced
either to SO2, to S or to H2S:
H2SO4 + 2H+ + 2e SO2 + 2H2O (S reduced from +6 to +4)
H2SO4 + 6H+ + 6e S + 4H2O (S reduced from +6 to 0)
H2SO4 + 8H + 8e H2S + 4H2O (S reduced from +6 to -2)
+
Cl- is not a strong reducing agent so is not oxidised by H2SO4. Only the acid-base
reaction takes place and HCl gas is formed:
H2SO4 + Cl- HSO4- + HCl (acid-base reaction)
White fumes of HCl will be seen. The fumes will turn blue litmus paper red.
Br- is a better reducing agent and is oxidised, but the sulphur in the H2SO4 is only
reduced from +6 to +4 (SO2). The acid-base reaction may also take place to an extent:
H2SO4 + Br- HSO4- + HBr (acid-base reaction)
H2SO4 + 2H+ + 2Br- SO2 + Br2 + 2H2O (redox reaction)
White fumes will be seen which turn blue litmus paper red. The red/orange colour of
bromine will also be seen.
I- is a good reducing agent and is oxidised, reducing the sulphur in the H2SO4 from
+6 to +4 (SO2), to 0 (S) or to -2 (H2S). The acid-base reaction may also take place to an
extent:
H2SO4 + I- HSO4- + HI (acid-base reaction)
H2SO4 + 6H + 6I S + 3I2 + 4H2O (redox reaction)
+ -
H2SO4 + 8H+ + 8I- H2S + 4I2 + 4H2O (redox reaction)
White fumes will be seen which turn blue litmus paper red. The purple colour of iodine
vapour will also be seen and there a will be a smell of rotten eggs due to the presence of
H2S.
The products of the reaction between the sodium halides and concentrated sulphuric acid
can be summarized in the following table:
Salt Products of reaction with concentrated Types of reaction occurring
sulphuric acid
NaCl HCl, NaHSO4 Acid-base
NaBr Br2, H2O, SO2, NaHSO4 Acid-base and redox
NaI I2, H2O, S, H2S, NaHSO4 Acid-base and redox