Assigning Oxidation Number Rules

1. The oxidation number of the atoms in any free, un-combined element is zero, e.g.
C, Al, H2, O2, O3, P4, S8.

2. The oxidation number of an element in a simple (monatomic) ion is equal to the

charge on the ion.

3. The sum of the oxidation numbers of all atoms in a compound is zero.

4. In a polyatomic ion, the sum of the oxidation numbers of the atoms is equal to the
charge on the ion.

5. Fluorine has an oxidation number of -1.

6. Hydrogen has an oxidation number of +1 in compounds unless it is combined

with metals, in which case it has on oxidation number of -1.

7. Oxygen usually has an oxidation number of -2. There are some exceptions:

a) Oxygen has an oxidation number of -1 in hydrogen peroxide, H2O2, and

in peroxides, which contain the O22- ion.

b) Oxygen has on oxidation number or -½ in superoxides which contain the O2-

ion.

c) When combined with fluorine in OF2, oxygen has an oxidation number of

+2.

8. The position of the element in the periodic table helps us to assign its oxidation
number when that element is in a compound.

If you cannot assign oxidation numbers to every element using the

rules, you will have to use rule 3 or 4 to determine the unknown
oxidation number arithmetically. If there are two unknowns, one of
them will be part of a polyatomic ion so you can use rule 4 and then
use rule 3 (or 4 again if the entire substance is charged).
 Worked Example 12.2 – Assigning Oxidation Numbers
Assign the oxidation state of each element in the following compounds of polyatomic ions.
Make sure you sure the RULES! Assigning oxidation numbers is a tool (or skill) you will need
to enable you to answer electrochemistry questions, so you need to able to do it almost
automatically. Now PRACTICE (without looking at the answers) until it is second nature! 

NO N 2H4

MgBr2 CuSO4

N2O3 HClO2

NH4Cl Cr2O72-

PO43- Fe2O3

SO3 AlN

SO32 C2H6O

HNO2 S2-

Zn(OH)42- Ca(NO3)2
Answers

NO N = +2 O = -2 N 2H4 N = -2 H = +1

MgBr2 Mg = +2 Br = -1 CuSO4 Cu = +2 S = +6 O = -2

N2O3 N = +3 O = -2 HClO2 H = +1 Cl = +3 O = -2

NH4Cl N = -3 H = +1 Cl = -1 Cr2O72- Cr = +6 O = -2

PO43- P = +5 O = -2 Fe2O3 Fe = +3 O = -2

SO3 S = +6 O = -2 AlN Al = +3 N = -3

SO32- S = +4 O = -2 C2H6O C = -2 H = +1 O = -2

HNO2 H = +1 N = +3 O = -2 S2- S = -2

Zn(OH)42- Zn = +2 O = -2 H = +1 Ca(NO3)2 Ca = +2 N = +5 O = -2