Oxidation number

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The oxidation number of an element in a molecule or complex is the charge that it would have if all shared electrons were assigned to the more electronegative elements in their bonds. It is used in the nomenclature of inorganic compounds. It is represented by a Roman numeral; the plus sign is omitted for positive oxidation numbers. The oxidation number is placed either as a right superscript to the element symbol, e.g. FeIII, or in parentheses after the name of the element, e.g. iron(III); in the latter case, there is no space between the element name and the oxidation number. The oxidation number can also be written with a number and either a + or - sign after it. If the element creates a positively charged ion, the oxidation number will have a + sign after it, (example-hydrogen 1+). If the element creates a negatively charged ion, the oxidation number will have a - sign after it, (example-oxygen 2-). The change in the oxidation number represents the number of electrons gained or lost in a chemical reaction.

The oxidation number is usually numerically equal to the oxidation state of the central atom. However, for a variety of reasons, the oxidation state of transition metals can be difficult to determine[1]. The most-accepted answer is that the electron pairs forming the coordination bonds are mostly associated with the ligands: this is a good approximation for most Werner-type complexes, but much less true for organometallic compounds as well as for certain hydrido complexes, dithiolene complexes and nitrosyl complexes.

[edit] Basic rules for the assigning of oxidation numbers

  1. All species in their elemental form are given the oxidation number of zero.
  2. All monoatomic ions have the same oxidation number as the charge on the ion. e.g. Mg2+ has the oxidation number of +2.
  3. All combined hydrogen has an oxidation number of +1 (except metal hydrides where its oxidation number is -1).
  4. All combined oxygen has an oxidation number of -2 (except peroxides where the oxidation number is -1 and compounds with fluorine where it can be positive).
  5. Combined fluorine always has an oxidation number of -1.
  6. In polyatomic species, the sum of the oxidation numbers of the element in the ion equals the charge on that species (we can use this to find the oxidation number of elements in polyatomic species).
  7. Group 1 elements such as K and Na and Group 2 elements such as Mg always have a +1 and +2 oxidation state in compounds, respectively.
  8. Halogens usually have an oxidation number of -1. Some exceptions are oxoanions such as chlorates.

A rough guide to follow is that you redistribute all the valence electrons of the atoms in a molecule such that the resulting ions have the "greatest overall stability", where the more electropositive atoms tend to give up their valence electrons which tend to go to the most electronegative elements first. That is why flourine in a molecule is always given oxidation number of -1. Fractional oxidation numbers can occur in some cases such as superoxides.

[edit] Example

The oxidation number of sulfur in sulfuric acid (H2SO4) can be calculated from the rules above. Because this is a polyatomic species, the individual oxidation numbers must sum to equal the overall charge, which in this case is zero. Hydrogen has an oxidation number of +1, so the sum of the oxidation numbers of H2 = 2. Oxygen has an oxidation number of -2, so the sum of oxidation numbers of O4 = -8. Since the overall sum must equal zero, the oxidation state of sulfur can be calculated as +6 (8-2).