Page 1 of 3 The mole concept

CHAPTER 1:

Below are a set of rules for assigning and using oxidation states:

1. An uncombined or a free element always has an oxidation state of zero. For example Na, K,
Cl2, O2, N2, S2, O3, P4, S8 all have oxidation states of zero.
2. The oxidation state of oxygen in compounds or ions is usually -2 except in peroxides (H2O2
= H – O – O – H, ROOR = R – O – O – R, Na2O2 = Na+ – O – O – Na+, K2S2O8 etc) where it
is -1 or in superoxides (KO2, CsO2 etc) where it is – ½. It is positive when it combines with
fluorine e.g +2 in F2O and +1 in F2O2 since fluorine is more electronegative than oxygen.
3. The oxidation state of an element in a compound is usually equal to its valency. For
example, the valency of sodium is +1 and that of chlorine is -1. In NaCl, Na has an
oxidation state of +1 while chlorine has an oxidation state of -1.
4. For monoatomic ions, the charge on the ion is equal to its oxidation state. The sulphide ion
(S2-) has an oxidation state of -2, while the aluminium ion(Al3+) has an oxidation state of +3.
5. The oxidation state of hydrogen is usually +1 in covalent compounds except in ionic
compounds (NaH, KH etc) and some complexes (NaBH4, LiAlH4 etc) where its oxidation
state is -1. For this reason, not all reactions involving the gain of hydrogen are reduction.
6. The algebraic sum of the oxidation states (O.S) of all the elements in a compound is zero . For
example, in H2SO4, (2 x O.S of H) + (1 x O.S of S) + (4 x O.S of O) = 0 since H2SO4 is neutral.
7. The algebraic sum of the oxidation states (O.S) of all the elements in a group of charged
atoms is equal to the charge on the ion. For example, if the oxidation state of phosphorus in
a phosphate ion (PO43-) is x and that of oxygen is y, then x + 4y = -3 since there are four
oxygen atoms, one phosphorus atom and the charge on the phosphate ion is -3.
8. In all compounds, fluorine has an oxidation state of -1.
9. In a compound or ion, the more electronegative element always has a negative oxidation
state. Chlorine is more electronegative than sodium. In NaCl, Cl has an oxidation state of -1
while Na has an oxidation state of +1. Tables of electronegativities and knowledge of the
variation of electronegativity on the periodic Table can used to determine the more
electronegative element in a compound.
An anomaly to rules assigning oxidation states is that some compounds may contain elements in
zero oxidation states e.g. nickel in the complex [Ni(CO)4], carbon in methanal (HCHO).

Balancing redox equations in acidic medium

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

A-Level chemistry notes 2014-2015 school year prepared by Nkemzi E.N

 Page 2 of 3 The mole concept

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) + é
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) + é
Red: Cr2O72-(aq) + 14H+(aq) + 6é → 2Cr3+(aq) + 7H2O(l).

Step 6: If the number of electrons lost in the oxidised 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) + é |x6
Red: Cr2O72-(aq) + 14H+(aq) + 6é → 2Cr3+(aq) + 7H2O(l). | x 1
Ox: 6Fe2+(aq) → 6Fe3+(aq) + 6é
Red: Cr2O72-(aq) + 14H+(aq) + 6é → 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) + 6é
Red: Cr2O72-(aq) + 14H+(aq) + 6é → 2Cr3+(aq) + 7H2O(l).

Overall: Cr2O72-(aq) + 6Fe2+(aq) + 14H+(aq) → 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l).

Balancing redox equations in basic medium

Consider balancing the redox equation below in basic medium.

Cr2O72-(aq) + Fe2+(aq) → Cr3+(aq) + Fe3+(aq).
The following steps should be followed when balancing redox equations in basic 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 appropriate number of electrons lost or gained to cause a change in oxidation
state of an element other than oxygen and hydrogen.
Ox: Fe2+(aq) → Fe3+(aq) + é
Red: Cr2O72-(aq) + 6é → 2Cr3+(aq).

- Step 5: To a half equation that contains both oxygen and hydrogen e.g. NO3- → NH3, add
water on the side that contains more oxygen or fewer hydrogen atoms. The number of water
molecules added is equal to the difference in the number of oxygen atoms on both sides
added to the difference in the number of hydrogen atoms on both sides of the equation.

A-Level chemistry notes 2014-2015 school year prepared by Nkemzi E.N

 Page 3 of 3 The mole concept

Ox: Fe2+(aq) → Fe3+(aq) + é

Red: Cr2O72-(aq) + 7H2O(l) + 6é → 2Cr3+(aq) + 14OH–(aq).

- Step 6: Add as many OH- ions on the side deficient in oxygen (richer in hydrogen) to balance
the number of hydrogen atoms on both sides of the equation.

Ox: Fe2+(aq) → Fe3+(aq) + é |x6

Red: Cr2O72-(aq) + 7H2O(l) + 6é → 2Cr3+(aq) + 14OH–(aq).| x 1

Step 7: If the number of electrons lost is not equal to the number of electrons gained, then
multiple the oxidised half and the reduced half by appropriate factors so as to make the
number of electrons lost is equal to the number of electrons gained.
Ox: Fe2+(aq) → Fe3+(aq) + é |x6
2- 3+ –
Red: Cr2O7 (aq) + 7H2O(l) + 6é → 2Cr (aq) + 14OH (aq).| x 1
Ox: 6Fe2+(aq) → 6Fe3+(aq) + 6é
Red: Cr2O72-(aq) + 7H2O(l) + 6é → 2Cr3+(aq) + 14OH–(aq).

Step 8: Add the two equations so as to cancel out the electrons leaving an overall balanced
equation with no electrons.
Ox: 6Fe2+(aq) → 6Fe3+(aq) + 6é
Red: Cr2O72-(aq) + 7H2O(l) + 6é → 2Cr3+(aq) + 14OH–(aq).

Overall: Cr2O72-(aq) + 6Fe2+(aq) + 7H2O(l) → 2Cr3+(aq) + 6Fe3+(aq) + 14OH–(aq).

Disproportionation reactions

In some redox reactions, the same species is simultaneously reduced and oxidised. For
example:
 Cl2(s) + H2O(l) → HCl (aq) + HOCl(aq).
0 -1 +1
 2Cu+(aq) → Cu(s) + Cu2+(aq).
 2Ge2+(aq) → Ge(s) + Ge4+(aq).
 2HCHO(aq) + OH–(aq) → CH3OH + HCOO–(aq) .

In the first equation, chlorine is said to disproportionate in water because it is reduced from
zero (0) to -1 HCl acid and oxidised from zero (0) to +1 in chloric (I) acid (HOCl).
Definition: A Disproportionation reaction is defined as a redox reaction in which a single
species undergoes simultaneous oxidation and reduction.
Disproportionation reaction can also be defined as a redox reaction in which a single
species simultaneously gains as many electrons as it loses.
The species that undergoes disproportionation has at least three oxidation states with zero (0)
inclusive. In a redox reaction, the number of electrons lost by the reducing agent is ALWAYS
equal to the number of electrons gained by the oxidising agent , a disproportionation reaction
can be given another definition.

Balancing disproportionation reactions

The disproportionation reaction is separated in the reduced and the oxidised halves and the
steps followed in balancing a redox reaction in acidic or basic medium applied.
Chlorine (Cl2) gas disproportionates in hot concentrated alkaline according to the equation
below. The ionic equation for the reaction is:
Cl2(g) + OH–(aq) → Cl–(aq) + ClO3–(aq).

A-Level chemistry notes 2014-2015 school year prepared by Nkemzi E.N