Oxidation numbers and redox equations

Recap of previous knowledge

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Define the terms: redox reaction, reduction and oxidation and half equation.
Balance the redox equation Mn7+ + Ti2+ Mn4+ + Ti4+.

Oxidation numbers (oxidation states)

Every element has a combining power. This combining power is called oxidation number or oxidation state .
Definition: An Oxidation state is defined as the charge an atom would have in a molecule or ion, if
electrons were completely transferred to the more electronegative atoms in the compound or ions.

Oxidation number rules

An oxidation number only refers to a single atom in a molecule or ion. There are a set of rules applied
in assigning oxidation numbers to atoms in compounds or ions. These rules are:
1. The oxidation state of free element (uncombined element) is zero. E.g. H 2, Cl2, P4, Cu etc.
2. In compounds, many atoms or ions have fixed oxidation numbers i.e.
- Group I elements always have +1 oxidation number in compounds
- Group II elements always have +2 oxidation number in compounds
- Fluorine always has -1 oxidation number in compounds
- Hydrogen has +1 oxidation number in compounds except in metal hydrides e.g LiH, NaH,
MgH2 etc where it has -1 oxidation number
- Oxygen has -2 oxidation number in compounds except in in peroxide links (OO), i.e. in
any compound that contains a peroxide e.g H2O2 where it is -1 and in F2O where it is +2.
3. The oxidation number of a monatomic (simple ) ion is the charge on the ion e.g. Na + has +1, S2has -2, Al3+ has +3 etc.
4. The sum of oxidation numbers of all atoms in a compound is zero.
5. The sum of oxidation numbers of all atom in a complex ion is equal to the charge of the ion.
6. In the molecules and ions, the more electronegative atom in given the negative oxidation numbers.
Positive oxidation number means electrons lost and negative oxidation state means electrons gain for a
perfect ionic compound.
Application of oxidation number rules
Oxidation number rules have a number of applications.
(a) Calculating oxidation states of compound
In a compound containing a metal and a non-metal, the metal always has a positive oxidation state
and non-metal negative. In a compound containing a non-metal and a non-metal, the less
electronegative non-metal always has a positive oxidation state while the more electronegative
non-metal negative.
Calculation of oxidation state of an element in a compound or ion:
The rules above are assigned in calculating the oxidation state of an element in a compound.
Example:
Calculate the oxidation state of sulphur in
(a) H2SO4
(b) SO32
(b) S2O32
Solution
Let the oxidation state of sulphur be y
(a)
2(+1) + y + 4(-2) = 0 => +2 + y - 8 = 0 => y - 6 = 0 => y = +6
(b)
y + 3(-2) = -2 => y - 6 = -2 => y = -2 + 6 => y = +4
(c)
2y + 3(-2) = -2 => 2y - 6 = -2 => 2y = -2 + 6 => 2y = + 4 => y = +2
Exercise:
1. Calculate the oxidation state of sulphur in
(a) SO3
(b) S4O62
(b) S2O82

The structure of S2O82 is

2. Calculate the oxidation state of phosphorus in

(a) P4O6
(b) POCl3
(b) PO43
(b) Balancing redox equations
Consider balancing the redox equation below in acidic medium.
Cr2O72-(aq) + Fe2+(aq) Cr3+(aq) + Fe3+(aq).
The following steps should be followed when balancing redox equations in acidic medium.
Step 1: Convert the equation given to an ionic equation if it is not an ionic equation.
Step 2: Separate the skeletal ionic equation into two half equations i.e. the oxidised half and the
reduced half.
Ox:
Fe2+(aq) Fe3+(aq).
Red:
Cr2O72-(aq) Cr3+(aq).
Step 3: In the half that atoms are not balanced, balance the atoms except oxygen and hydrogen.
Ox:
Fe2+(aq) Fe3+(aq).
Red:
Cr2O72-(aq) 2Cr3+(aq).
Step 4: Add an appropriate number of water molecules (H2O) to the side of a half equation
deficient in oxygen in order to balance oxygen on both side. Add an appropriate number of
hydrogen ions (H+) to the side of a half equation richer in oxygen in order to balance the total
number of hydrogen atoms in water just added.
Ox:
Fe2+(aq) Fe3+(aq) +
Red:
Cr2O72-(aq) + 14H+(aq) 2Cr3+(aq) + 7H2O(l).
Step 5: Add as many electrons as possible so as to balance charges on both sides.
Ox:
Fe2+(aq) Fe3+(aq) +
Red:
Cr2O72-(aq) + 14H+(aq) + 6 2Cr3+(aq) + 7H2O(l).
Step 6: If the number of electrons lost in the oxidise half is not equal to the number of electrons
gained in the reduced half, then multiple the oxidised half and the reduced half by appropriate
factors in order to make the number of electrons lost equal to the number of electrons gained.
Ox:
Fe2+(aq) Fe3+(aq) +
|x6
Red:
Cr2O72-(aq) + 14H+(aq) + 6 2Cr3+(aq) + 7H2O(l).
|x1
2+
3+
Ox:
6Fe (aq) 6Fe (aq) + 6
Red:
Cr2O72-(aq) + 14H+(aq) + 6 2Cr3+(aq) + 7H2O(l).
Step 7: Add the two equations so as to cancel out the electrons leaving an overall balanced
equation with no electrons.
Ox:
6Fe2+(aq) 6Fe3+(aq) + 6
Red:
Cr2O72-(aq) + 14H+(aq) + 6 2Cr3+(aq) + 7H2O(l).
Overall: Cr2O72-(aq) + 6Fe2+(aq) + 14H+(aq) 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l).
Assignment
Balance the following redox equations strictly in acidic medium:
a) MnO4(aq) + Fe2+(aq) MnO2(s) + Fe3+(aq).
b) Cr2O72 (aq) + C2O42 (aq) Cr3+(aq) + CO2(g).
c) S8(s) + NO3(aq) SO2 (g) + NO(g).
d) Cr2O72 (aq) + SO2(g) Cr3+ (g) + SO42(g).
e) S2(aq) + NO3(aq) S8(s) + NO(g).

Assignment

Definition: A redox equation is defined as an equation in which the oxidation state of at least one
species changes from the reactant side to the product side.
Note that in a disproportionation reaction, only the oxidation state of one species changes.

(c)