Assigning Oxidation Numbers (or state)

1.    The oxidation number of an element is zero(0).

  Cu(s) Mg(s) O2(g) S8(s) Hg(l)
Ox#  0  0  0  0  0
2.    For monatomic ions, the oxidation number is the same as the charge on the ion.
  Na+(aq) Cu2+(aq) Fe3+(aq) Cl-(aq) S2-(aq) N3-(aq)
Ox# +1 +2 +3 -1 -2 -3
3.    In binary compounds (or polyatomic ions), the second element is assigned a negative
       oxidation number, usually the same as the charge on its monatomic ion.
  SCl2 SiBr4 CS2 P4S4 CSe2 CN- S2N+
Ox#    -1     -1   -2    -2   -2   -3    -3

a.    F always -1.

  OF2 CF4 BF4- ClF6+
Ox#   -1   -1   -1    -1
b.    O usually -2 (except peroxide -1 and superoxide -1/2).  Peroxides and superoxides
       can only be determined if the cation they are associated with has a fixed charge (H,
       alkali metals or alkaline-earth metals).
  H2O P2O5 VO2+ UO22+ ClO3- SO42- PO43-
Ox#     -2     -2   -2   -2    -2   -2   -2

 
  H2O2 BaO2 Na2O2 KO2
Ox# +1 -1 +2 -1 +1 -1 +1 -1/2
c.    Hydrogen is -1 only when combined with a metal, hydride ion.  H is +1 when
       written first (usually acids).
  LiH CaH2 AlH4-
Ox#    -1     -1    -1

 
  H2O HCl H2SO4 H3PO4
Ox# +1 +1 +1 +1
4.    The sum of oxidation numbers in a compound or polyatomic ion is equal to the overall
       charge on the compound (0) or the ion.
  SCl2 SiBr4 CS2 P4S4 CSe2 CN- S2N+
Ox# +2 -1 +4 -1 +4 -2 +2 -2  +4 -2 +2 -3 +2 -3 

 
  OF2 CF4 BF4- ClF6+
Ox# +2 -1 +4 -1 +3 -1 +7 -1

 
  H2O P2O5 VO2+ UO22+ ClO3- SO42- PO43-
Ox# +1 -2 +5 -2 +4 -2 +6 -2 +5 -2 +6 -2 +5 -2

 
  LiH CaH2 AlH4-
Ox# +1 -1 +2 -1 +3 -1

 
  H2O HCl H2SO4 H3PO4
Ox# +1 -2 +1 -1 +1 +6 -2 +1 +5 -2


These rules do work as simply with molecular compounds with more than two types of atoms.

For example, C2H6O2, and many other organic compounds.