Oxidation numbered method:

Before we will get to explanation very important disclaimer: oxidation numbers don't exist. They were invented
to help in charge accounting needed when balancing redox reaction equations, but they don't refer to any real
life chemical concept.
The general idea behind the oxidation numbers (ON) method for balancing chemical equations is that electrons
are transferred between charged atoms. These charges - assigned to individual atoms - are called oxidation
numbers, just to remind you that they don't reflect real structure of the reagents.
There are several simple rules used for assigning oxidation numbers to every atom present in any compound
First of all, charged mono atomic ion has oxidation number equal to its charge. Thus Na
+
has oxidation
number +1, Fe
3+
has oxidation number +3, F
-
has oxidation number of -1 and S
2-
has oxidation number
of -2.
Second rule says that the oxidation number of a free element is always 0. Thus oxidation number of
solid, metallic Cu is 0, oxidation number of O in O
2
is 0, the same holds for S in S
8
and so on.
Oxygen in almost all compounds has oxidation number -2.
Hydrogen in almost all compounds has oxidation number +1.
Some elements usually have the same oxidation number in their compounds:
alkali metals - Li, Na, K, Rb, Cs - oxidation numbers are +1
alkaline earth metals - Be, Mg, Ca, Sr, Ba - oxidation numbers are +2
halogens (except when they form compounds with oxygen or one another) - oxidation numbers are -1
(always true for fluorine)
Last rule says that the charge of the ion or molecule equals sum of oxidation numbers of all atoms.

There are some exceptions to the rules 3 and 4 - for example oxygen in peroxides has oxidation number of -1, it
is also not -2 in compounds with fluorine (where F is always -1), hydrogen in hydrides has oxidation number -1.
Before we will try to balance any equations let's use above rules to assign oxidation numbers to atoms in several
substances.
For example - what is oxidation number of sulfur in SO
2
? Particle is not charged, so oxidation number of sulfur
must equal sum of oxidation numbers of oxygens, but with the opposite sign. Oxygen oxidation number is -2,
there are two oxygens - that gives -4 together, so sulfur must have ON=+4.
What is oxidation number of atoms in CrO
4
2-
? Oxygen is -2 and there are 4 oxygens - that gives overall of -8,
ion has charge of -2, so central atom must have ON=+6.
How do we use oxidation numbers for balancing? First of all, we have to understand that oxidation means
increase of oxidation number, while reduction means decrease of oxidation number. In both cases change of
oxidation number is due to electrons lost (oxidation) or gained (reduction). We calculate oxidation numbers for
all atoms present in the reaction equation (note that it is not that hard as it sounds, as for most atoms oxidation
numbers will not change) and we look for a ratio that makes the number of electrons lost equal to the number of
electrons gained. That gives us additional information needed for reaction balancing.
Let's try with following reaction:
KIO
3
+ KI + H
2
SO
4
-> K
2
SO
4
+ H
2
O + I
2

First of all - we don't need any spectators here, as they are only making things look more difficult then they are
in reality. Quick glance tells us that the net ionic reaction is
IO
3
-
+ I
-
+ H
+
-> H
2
O + I
2

Looks like IO
3
-
is oxidizing agent here and I
-
is reducting agent. I
-
has oxidation number of -1, iodine in IO
3
-
has
oxidation number of +5. On the right side in I
2
both iodine atoms have oxidation number 0. It means that iodine
in IO
3
-
must gain 5 electrons. These electrons come from I
-
- one for every I
-
ion. Assuming (just like we do in
the inspection method) that IO
3
-
is the most complicated molecule and it's coefficient is 1 we will need five I
-

for the redox process to complete:
1IO
3
-
+ 5I
-
+ H
+
-> H
2
O + I
2

Now that the ratio between oxidizer and reducing agent is known we use simple techniques we know from the
inspection method to balance remaining elements. There are six atoms of iodine on the left, so we need three I
2

molecules to balance iodine:
1IO
3
-
+ 5I
-
+ H
+
-> H
2
O + 3I
2

And the final, trivial step is balancing oxygen, hydrogen and water:
IO
3
-
+ 5I
-
+ 6H
+
-> 3H
2
O + 3I
2

Other case we can try is oxidation of Mn
2+
with NaBiO
3
in acidic conditions:
Mn
2+
+ BiO
3
-
+ H
+
-> MnO
4
-
+ Bi
3+
+ H
2
O
Using methods for oxidation numbers calculation we can easily check that manganese is oxidized from +2 to +7
(freeing five electrons) and bismuth is reduced from +5 to +3 (accepting two electrons). To balance electrons
transferred we can put coefficients 2 and 5 on the left side of reaction equation:
2Mn
2+
+ 5BiO
3
-
+ H
+
-> MnO
4
-
+ Bi
3+
+ H
2
O
Rest can be balanced by inspection and is not difficult to do, yielding:
2Mn
2+
+ 5BiO
3
-
+ 14H
+
-> 2MnO
4
-
+ 5Bi
3+
+ 7H
2
O
Now the same equation can be also easily balanced as a full (non net-ionic) version:
1. 4MnSO
4
+ 10NaBiO
3
+ 14H
2
SO
4
-> 4NaMnO
4
+ ion electron method
5Bi
2
(SO
4
)
3
+ 14H
2
O
ion electron method

The balancing of a chemical equation by ion-electron method (using half reactions) is done according to the
following steps.
Find the elements whose oxidation numbers are changed. Choose the substance, which acts as an
oxidizing agent and one that acts as a reducing agent.
Separate the complete equation into two half reactions, one for the change undergone by the oxidizing
agent and the other for the change undergone by the reducing agent.
Balance half equations by the following steps:
2. Balance all atoms other than H and O.
3. Calculate the oxidation number on both sides of the equation and add electrons to whichever side is
necessary, to make up the difference.
4. Balance the half equation so that both sides get the same charge.
5. Add water molecules to complete the balancing of the equation .ion electron method
Add two balanced half equations. Multiply one or both half equations by suitable numbers so that on
adding the two equations, the electrons are balanced.
Redox reactions take place in all the three media acidic or basic or neutral. If H
+
ions appear on either side of
the equation, the reaction takes place in acidic medium. If OH
-
ions appear on either side of the equation, the
solution is basic. If neither H
+
nor OH
-
ions are present, the reaction occurs in neutral solution.
For balancing redox reactions involving acidic and basic media, the method has to be modified slightly. The
steps are summarized by the following flowchart.