Oxidation and Reduction (Redox) Reactions

Generally, a redox reaction is one in which electrons are transferred between species or in which atoms change oxidation
states. More specifically and depending on what happens exactly during the reaction, oxidation and reduction can be defined
in a number of ways as seen in the table below:

Oxidation Reduction

1. Addition of oxygen Removal of oxygen

2. Removal of hydrogen Addition of hydrogen

3. Addition of electronegative elements Removal of electronegative elements

4. Removal of electrons Addition of electrons

5. Increase in oxidation number Decrease in oxidation number

Oxidation Numbers
The oxidation number (o.n.) or oxidation state (o.s.) of an atom in a substance is the actual charge of the atom if it exists as a
monatomic ion; it is the hypothetical charge assigned to an atom in a substance taking into account the relative
electronegativities of other atoms in the substance.
Rules for Assigning Oxidation Numbers
1. The oxidation state (o.s.) of an atom of an element in an uncombined state is zero e.g. atoms in S, K, Na, Cl2, O2 etc have
zero oxidation states.
2. The o.s. of an ion equals the charge on the ion e.g. Na+ = +1; Cl- = -1; Al3+ = +3, SO42- = -2; NH4+ = +1.
3. The o.s. of some elements in their compounds are the same e.g. elements in Group I (Li, Na, K, …) have o.s. of +1, while
those in Group II (Be, Mg, Ca, ...) have o.s. of +2.
4. The o.s. of oxygen is -2 in most of its compounds; an exception is O in peroxides where the o.o. is -1 and in combination
with F to form OF2 where it has o.s. of +2. The super oxides (LiO2, NaO2, RbO2) are unusual where oxygen has a fractional
o.s. of -½.
5. The o.s. of hydrogen is +1 in most of its compounds except in binary compounds (metal hydrides) e.g. CaH2 where it has
-1 o.s.
6. The o.s. of F is -1 in all of its compound; each of the other halogens (Cl, Br, I) has o.s. of -1 in binary compounds, except
when the other element is another halogen above it in the Periodic Table or the other element is oxygen.
7. The algebraic sum of o.s. of all atoms in a neutral molecule (e.g. KMnO4, Na2CO3, Na2Cr2O7, etc) is zero.
8. In a complex ion, the algebraic sum of o.s. of all the atoms is equal to the charge on the ion e.g. Cr2O72- = -2
NOTE:
1. Some elements have the capacities of exhibiting several o.s. For example, S in H2S, S, SCl2, H2SO3 and H2SO4 has o.s. of
-2, 0, +2, +4 and +6 respectively, while Cl has o.s. of -2, +1, +4, +5 and + 7 respectively in HCl, Cl2O7, ClO2, KClO3 and
KClO4.
2. The same element in a compound can have different o.s. For example, N in NH4NO3 has -3 and +5 o.s., while Fe in Fe3O4
(i.e. FeIIFe2IIIO4).
3. Oxidation numbers (other than zero) are always written as directed numbers.
 Example:
Calculate the oxidation number of (a) Mn in KMnO4 and (b) Cr in Cr2O72- [K = +1, O = -2]

Solution
(a) KMnO4 = 0
i.e. K + Mn + 4 (O) = 0
i.e. +1 + Mn +4(-2) = 0
:- Mn = +7

(b) Cr2O72- = -2
i.e. 2Cr + 7(O) = -2
i.e. 2Cr + 7(-2) = -2
i.e. 2Cr -14 = -2
⇒2Cr = +12
:- Cr = +6

Exercise
Determine the oxidation number(s) of the underlined elements in the following compounds or ions:
1. K2CrO4 5. P2O72-
2. BaCrO4 6. S2O32-
3. Na3PO4 7. Hg2Cl2
4. K4Fe(CN)6 8. HgCl2
[K +1, O = -2, Ba = +2, Na = +1, CN- = -1, Cl = -1]