You need to determine the oxidation state of each element. Oxygen usually has an ox state of -2 ( except in Hydrogen Peroxide H2O2 and OF2 ) while Hydrogen's ox state is +1 with non-metals. The concept of assigning Oxidation states is to keep track of electrons in Redox reactions.
Next, you can determine which substance is being oxidized ( loses electrons ) and which substance is being reduced ( gains electrons ).
You write down the oxidation half reaction and the reduction half reaction, deduce the net ionic equation, and then balance the Oxygens by adding H2O and you balance hydrogens by adding:
1-H+ if the medium is acidic ( as is your case )
2-OH- if the medium is basic
3-none if the medium is neutral
The best way to understand this is to solve many problems.
Let's consider the rxn you gave :
SO32- + MnO4- + H+ <---> Mn2+ + SO42- + H2O
In this case, H+ is given as well as H2O. Sometimes, it might be only mentioned that the medium is acidic, and u would conclude that there's an H+.
For SO32-:
Ox state of O = -2
Ox state of S = x
x + (-2)(3) = -2 ( total ox state of a molecule = charge of the molecule )
x = ox state of S = +4
Let's see what happens to Sulphur in the products side.
SO42-:
Ox state of O = -2
Ox state of S = x
x + (-2)(4) = -2 ( total ox state of a molecule = charge of the molecule )
x = ox state of S = +6
Therefore, for S, the ox state has increased from +4 to +6. We deduce that Sulphur was oxidized by losing 2 electrons.
The Oxidation half-reaction which takes place at the anode :
For SO32- <---> SO42- + 2e
Next, we see if Mn is being reduced.
MnO4-:
Ox state of O = -2
Ox state of Mn = x
x + (-2)(4) = -1
x = +7
In the products' side, for Mn2+ :
Ox state of Mn = +2
Obviously, Mn has been reduced by gaining 5 electrons. ( Ox state reduced from +7 to +2 )
We write the Reduction half-rxn which takes place at the Cathode:
MnO4- + 5e <---> Mn2+
We have thus established the following so far :
Ox : SO32- <---> SO42- + 2e
Red : MnO4- + 5e <---> Mn2+
Multiply the 1st by 5 and the 2nd by 2 inorder to cancel the electrons when adding both half-reactions.
5 SO32- + 2 MnO4- <---> 5 SO42- + 2 Mn2+
Now that Mn and S are balanced, all that's left is to balance the Oxygen & Hydrogen atoms.
On the reactants' side, we have 23 O atoms. On the products' side, we have 20 O atoms. Hence, we add 3 H2O molecules to the right.
5 SO32- + 2 MnO4- <---> 5 SO42- + 2 Mn2+ + 3 H2O
Check for Hydrogen:
On the reactants' side, no H atoms
On the products' side, 6 H atoms.
Hence, we add 6 H+
Net ionic Equation : 5 SO32- + 2 MnO4- + 6 H+ <---> 5 SO42- + 2 Mn2+ + 3 H2O
Notice : the equation is not only balanced from an atomic perspective, but also electrically balanced. The charges cancel on both sides, try it out yourself.