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1.9.2 Oxidation States: The Rules

Definition of Oxidation State

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The oxidation state (or oxidation number) of an atom represents its hypothetical charge if all bonds in a compound were considered completely ionic. This concept helps track electron transfers in redox reactions and determine whether oxidation or reduction has occurred.

Rules for Assigning Oxidation States

Uncombined Elements

The oxidation state of any element in its uncombined form (i.e., not bonded to any other element) is 0.

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Example: The oxidation state of O2O_2 (oxygen molecule) or LiLi (lithium atom) is 0.

Monatomic Ions

The oxidation state of a simple monatomic ion is equal to the charge on the ion.

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Example: The oxidation state of Li+Li^+ is +1.

Compounds

In a neutral compound, the sum of the oxidation states of all atoms must equal 0.

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Example: In sodium chloride NaClNaCl, Na+Na^+ has an oxidation state of +1

ClCl^- has an oxidation state of -1

Therefore +1+(1)=0+1 + (-1) = 0

Polyatomic Ions

In a polyatomic ion, the sum of the oxidation states of all atoms must equal the overall charge of the ion.

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Example: In the sulfate ion SO42SO_4^{2-}, oxygen typically has an oxidation state of -2, and the total for four oxygens is -8.

Therefore, sulfur must have an oxidation state of +6 to balance the charge (i.e., +6+(8)=2+6 + (-8) = -2).

Oxygen

  • Oxygen typically has an oxidation state of -2 in most compounds.
  • Exceptions:
    • In peroxides (e.g., H2O2H_2O_2), oxygen has an oxidation state of -1.
    • In oxygen difluoride OF2OF_2, oxygen has an oxidation state of +2.

Hydrogen

  • Hydrogen usually has an oxidation state of +1.
  • Exception: In metal hydrides (e.g., NaHNaH), hydrogen has an oxidation state of -1.

Group 1 and Group 2 Elements

  • Group 1 elements (e.g., NaNa) always have an oxidation state of +1 in their compounds.
  • Group 2 elements (e.g., MgMg) always have an oxidation state of +2.

Electronegativity

In binary compounds (compounds of two elements), the more electronegative element is assigned the negative oxidation state.

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Example: In HClHCl, chlorine is more electronegative and has an oxidation state of -1.

While hydrogen has +1.

Transition Metals and p-Block Elements

Transition metals and p-block elements can have variable oxidation states. Their oxidation state in a given compound is usually indicated using Roman numerals.

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Example: Cu2+Cu^{2+} is referred to as copper(II), with an oxidation state of +2.

Examples of Finding Oxidation States

From Formulae

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Example: Find the oxidation state of zinc in Zn(OH)2Zn(OH)_2

Oxygen has an oxidation state of -2, and hydrogen is +1.

The overall charge of Zn(OH)2Zn(OH)_2 is 0.

Therefore:

x+2(+1)+2(2)=0x + 2(+1) + 2(-2) = 0x=+2x = +2

Thus, zinc has an oxidation state of +2 in Zn(OH)2Zn(OH)_2

From Systematic Names

Transition metals can have multiple oxidation states, and these are shown using Roman numerals.

  • Copper(II) means copper has an oxidation state of +2.
  • Copper(III) means copper has an oxidation state of +3.
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